2,4,5-trisubstituted phenylketo-enols for use as pesticides and herbicides

ABSTRACT

The invention relates to new phenyl-substituted cyclic ketoenols of the formula (I)  
                 
 
     in which  
     Het represents one of the groups  
                 
 
     wherein A, B, D, G, X, Y and Z have the meaning given in the description, several processes and intermediate products for their preparation and their use as pest control agents and herbicides.

[0001] The invention relates to new phenyl-substituted cyclic ketoenols,several processes and intermediate products for their preparation andtheir use as pest control agents and herbicides.

[0002] It has already been disclosed that certain phenyl-substitutedcyclic ketoenols are active as insecticides, acaricides and/orherbicides.

[0003] Pharmaceutical properties have already been described for3-acyl-pyrrolidine-2,4-diones (S. Suzuki et al. Chem. Pharm. Bull. 151120 (1967)). Furthermore, N-phenylpyrrolidine-2,4-diones have beensynthesized by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem.1985, 1095). No biological activity has been described for thesecompounds.

[0004] EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of similarstructure (3-aryl-pyrrolidine-2,4-diones), of which, however, noherbicidal, insecticidal or acaricidal action has been disclosed. Knowncompounds which have a herbicidal, insecticidal or acaricidal action areunsubstituted, bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives(EP-A-355 599 and EP-A-415 211) and substituted monocyclic3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442077).

[0005] Compounds which are furthermore known are polycyclic3-arylpyrrolidine-2,4-dione derivatives (EP-A-442 073) and1H-arylpyrrolidine-dione derivatives (EP-A-456 063, EP-A-521 334,EP-A-596 298, EP-A-613 884, EP-A-613 885, DE 44 40 594, WO 94/01 997 andWO 95/01 358).

[0006] It is known that certain substituted Δ³-dihydrofuran-2-onederivatives have herbicidal properties (cf. DE-A-4 014 420). Thesynthesis of the tetronic acid derivatives used as starting compounds(such as, for example,3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-Δ³-dihydrofuran-2-one)is likewise described in DE-A-4 014 420. Compounds of similar structure,without an insecticidal and/or acaricidal activity being mentioned, areknown from the publication Campbell et al., J. Chem. Soc., Perkin Trans.1, 1985, (8) 1567-76. 3-Aryl-Δ³-dihydrofuranone derivatives havingherbicidal, acaricidal and insecticidal properties are furthermore knownfrom EP-A-528 156, EP-A 0 647 637 and WO 95/26345.

[0007] Certain phenyl-pyrone derivatives which are unsubstituted in thephenyl ring have already been disclosed (cf. A. M. Chirazi, T. Kappe andE. Ziegler, Arch. Pharm. 309, 558 (1976) and K. -H. Boltze and K.Heidenbluth, Chem. Ber. 91, 2849), no possible usefulness of thesecompounds as pest control agents being mentioned. Phenyl-pyronederivatives which are substituted in the phenyl ring and haveherbicidal, acaricidal and insecticidal properties are described inEP-A-588 137.

[0008] Certain 5-phenyl-1,3-thiazine derivatives which are unsubstitutedin the phenyl ring have already been disclosed (cf E. Ziegler and E.Steiner, Monatsh. 95, 147 (1964), R. Ketcham, T. Kappe and E. Ziegler,J. Heterocycl. Chem. 10, 223 (1973)), no possible use as pest controlagents being mentioned for these compounds. 5-Phenyl-1,3-thiazinederivatives which are substituted in the phenyl ring and have aherbicidal, acaricidal and insecticidal action are described in WO 94/14785.

[0009] However, the acaricidal and insecticidal activity and/or range ofaction and the plant tolerance of these compounds, in particular withrespect to crop plants, is not always adequate.

[0010] New compounds of the formula (I)

[0011] in which

[0012] X represents halogen, alkyl, alkenyl, alkinyl, alkoxy,halogenoalkyl, halogenoalkoxy, cyano or nitro,

[0013] Y represents hydrogen, halogen, alkyl, alkoxy, halogenoalkyl,halogenoalkoxy, cyano or nitro,

[0014] Z represents halogen, alkyl, alkoxy, halogenoalkyl,halogenoalkoxy, hydroxyl, cyano, nitro or in each case optionallysubstituted phenoxy, phenylthio, 5-to 6-membered hetaryloxy, 5- to6-membered hetarylthio, phenylalkyloxy or phenylalkylthio or

[0015] Y and Z, together with the carbon atom to which they are bonded,represent a cyclic radical which is optionally substituted andoptionally interrupted by heteroatoms, wherein X has one of theabovementioned meanings,

[0016] Het represents one of the groups

[0017] wherein

[0018] A represents hydrogen, or represents alkyl, alkenyl, alkoxyalkyl,polyalkoxyalkyl or alkylthioalkyl which are in each case optionallysubstituted by halogen, or represents in each case saturated orunsaturated and optionally substituted cycloalkyl or heterocyclyl, orrepresents aryl, arylalkyl or hetaryl which are in each case optionallysubstituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy,cyano or nitro,

[0019] B represents hydrogen, alkyl or alkoxyalkyl, or

[0020] A and B, together with the carbon atom to which they are bonded,represent a saturated or unsaturated, optionally substituted carbocyclicor heterocyclic radical,

[0021] D represents hydrogen, or represents an optionally substitutedradical from the series consisting of alkyl, alkenyl, alkinyl,alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturatedcycloalkyl, saturated or unsaturated heterocyclyl, arylalkyl, aryl,hetarylalkyl or hetaryl, or

[0022] A and D, together with the atoms to which they are bonded,represent a carbocyclic or heterocyclic radical which is in each caseoptionally substituted,

[0023] G represents hydrogen (a), or represents one of the groups

[0024] wherein

[0025] E represents one metal ion equivalent or an ammonium ion,

[0026] L represents oxygen or sulphur,

[0027] M represents oxygen or sulphur,

[0028] R¹ represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl orpolyalkoxyalkyl which are in each case optionally substituted byhalogen, or represents cycloalkyl or heterocyclyl which are in each caseoptionally substituted by halogen, alkyl or alkoxy, or represents ineach case optionally substituted phenyl, phenylalkyl, hetaryl,phenoxyalkyl or hetaryloxyalkyl,

[0029] R² represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkylwhich are in each case optionally substituted by halogen, or representsin each case optionally substituted cycloalkyl, phenyl or benzyl,

[0030] R³, R⁴ and R⁵ independently of one another represent alkyl,alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio orcycloalkylthio which are in each case optionally substituted by halogen,or represent in each case optionally substituted phenyl, phenoxy orphenylthio, and

[0031] R⁶ and R⁷ independently of one another represent hydrogen, orrepresent alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl which are ineach case optionally substituted by halogen, or represent in each caseoptionally substituted phenyl or benzyl, or, together with the N atom towhich they are bonded, form a cyclic radical which optionally containsoxygen or sulphur and is optionally substituted,

[0032] have now been found.

[0033] The compounds of the formula (I) can be in the form of geometricand/or optical isomers or isomer mixtures of varying composition, alsodepending on the nature of the substituents, and these can optionally beseparated in the customary manner. The present invention relates both tothe pure isomers and to the isomer mixtures, their preparation and useand compositions comprising them. For simplicity, however, reference isalways made below to compounds of the formula (I), although this meansboth the pure compounds and, where appropriate, also mixtures withdifferent contents of isomeric compounds.

[0034] Incorporating the meanings (1) to (5) of the group Het, thefollowing main structures (I-1) to (I-5) result:

[0035] wherein

[0036] A, B, D, G, X, Y and Z have the abovementioned meaning.

[0037] Incorporating the various meanings (a), (b), (c), (d), (e), (f)and (g) of the group G, the following main structures (I-1-a) to (I-1-g)result if Het represents the group (1)

[0038] wherein

[0039] A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have theabove-mentioned meanings.

[0040] Incorporating the various meanings (a), (b), (c), (d), (e), (f)and (g) of the group G, the following main structures (I-2-a) to (I-2-g)result if Het represents the group (2)

[0041] wherein

[0042] A, B, E, L, M, X, Y, Z, R¹, R², R, R⁴, R⁵, R⁶ and R⁷ have theabove-mentioned meaning.

[0043] Incorporating the various meanings (a), (b), (c), (d), (e), (f)and (g) of the group G, the following main structures (I-3-a) to (I-3-g)result if Het represents the group (3)

[0044] wherein

[0045] A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have theabove-mentioned meaning.

[0046] The compounds of the formula (I-4) can be present in the twoisomeric forms of the formulae (I-4)_(a) and (I-4)_(b), depending on theposition of the substituent G

[0047] which is illustrated by the broken line in the formula (I-4).

[0048] The compounds of the formulae (I-4)_(a) and (I-4)_(b) can bepresent both in the form of mixtures and in the form of their pureisomers. Mixtures of the compounds of the formulae (I-4)_(a) and(I-4)_(b) can be separated, where appropriate, by physical methods in amanner known per se, for example by chromatographic methods.

[0049] For reasons of better clarity, in each case only one of thepossible isomers is mentioned below. This does not mean that thecompounds cannot be present, where appropriate, in the form of theisomer mixtures or in the other particular isomeric form.

[0050] Incorporating the various meanings (a), (b), (c), (d), (e), (f)and (g) of the group G, the following main structures (I-4-a) to (I-4-g)result if Het represents the group (4)

[0051] wherein

[0052] A, D, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have theabove-mentioned meanings.

[0053] Incorporating the various meanings (a), (b), (c), (d), (e), (f)and (g) of the group G, the following main structures (I-5-a) to (I-5-g)result if Het represents the group (5)

[0054] wherein

[0055] A, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have theabove-mentioned meanings.

[0056] It has furthermore been found that the new compounds of theformula (I) are obtained by one of the processes described below:

[0057] (A) compounds of the formula (I-1-a)

[0058] in which

[0059] A, B, X, Y and Z have the abovementioned meanings,

[0060] are obtained when

[0061] compounds of the formula (II)

[0062] in which

[0063] A, B, X, Y and Z have the abovementioned meanings and

[0064] R⁸ represents alkyl (preferably C₁-C₆-alkyl)

[0065] are subjected to an intramolecular condensation reaction in thepresence of a diluent and in the presence of a base.

[0066] (B) It has furthermore been found that compounds of the formula(I-2-a)

[0067] in which

[0068] A, B, X, Y and Z have the abovementioned meanings,

[0069] are obtained when

[0070] compounds of the formula (III)

[0071] in which

[0072] A, B, X, Y, Z and R⁸ have the abovementioned meanings,

[0073] are subjected to an intramolecular condensation reaction in thepresence of a diluent and in the presence of a base.

[0074] (C) It has furthermore been found that compounds of the formula(I-3-a)

[0075] in which

[0076] A, B, X, Y and Z have the abovementioned meanings,

[0077] are obtained when

[0078] compounds of the formula (IV)

[0079] in which

[0080] A, B, X, Y, Z and R⁸ have the abovementioned meanings and

[0081] W represents hydrogen, halogen, alkyl (preferably C₁-C₆-alkyl) oralkoxy (preferably C₁-C₈-alkoxy),

[0082] are subjected to intramolecular cyclization, if appropriate inthe presence of a diluent and in the presence of an acid.

[0083] (D) It has furthermore been found that compounds of the formula(I-4-a)

[0084] in which

[0085] A, D, X, Y and Z have the abovementioned meanings,

[0086] are obtained when

[0087] compounds of the formula (V)

[0088] in which

[0089] A and D have the abovementioned meanings,

[0090] or silylenol ethers thereof of the formula (Va)

[0091] in which

[0092] A and D have the abovementioned meaning and

[0093] R^(8′) represents alkyl (preferably methyl),

[0094] are reacted with compounds of the formula (VI)

[0095] in which

[0096] X, Y and Z have the abovementioned meanings and

[0097] Hal represents halogen (preferably chlorine or bromine),

[0098] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid acceptor.

[0099] (E) It has furthermore been found that the compounds of theformula (I-5-a)

[0100] in which

[0101] A, X, Y and Z have the abovementioned meanings,

[0102] are obtained when compounds of the formula (VII)

[0103] in which

[0104] A has the abovementioned meaning,

[0105] are reacted with compounds of the formula (VI)

[0106] in which

[0107] Hal, X, Y and Z have the abovementioned meanings,

[0108] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid acceptor.

[0109] It has furthermore been found

[0110] (F) that the compounds of the formulae (I-1-b) to (I-5-b) shownabove, in which A, B, D, R¹, X, Y and Z have the abovementionedmeanings, are obtained when compounds of the formulae (I-1-a) to (I-5-a)shown above, in which A, B, D, X, Y and Z have the abovementionedmeanings, are reacted

[0111] α) with acid halides of the formula (VIII)

[0112] in which

[0113] R¹ has the abovementioned meaning and

[0114] Hal represents halogen (in particular chlorine or bromine), or

[0115] β) with carboxylic acid anhydrides of the formula (IX)

R¹—CO—O—CO—R¹  (IX)

[0116] in which

[0117] R¹ has the abovementioned meaning,

[0118] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid-binding agent;

[0119] (G) that the compounds of the formulae (I-1-c) to (I-5-c) shownabove, in which A, B, D, R², M, X, Y and Z have the abovementionedmeanings and L represents oxygen, are obtained when compounds of theformulae (I-1-a) to (I-5-a) shown above, in which A, B, D, X, Y and Zhave the abovementioned meanings, in each case are reacted

[0120] with chloroformic acid esters or chloroformic acid thioesters ofthe formula (X)

R²-M-CO—Cl  (X)

[0121] in which

[0122] R² and M have the abovementioned meanings,

[0123] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid-binding agent;

[0124] (H) that compounds of the formulae (I-1-c) to (I-5-c) shownabove, in which A, B, D, R, M, X, Y and Z have the abovementionedmeanings and L represents sulphur, are obtained when compounds of theformulae (I-1-a) to (I-5-a) shown above, in which A, B, D, X, Y and Zhave the abovementioned meanings, in each case

[0125] α) are reacted with chloromonothioformic acid esters orchlorodithioformic acid esters of the formula (XI)

[0126] in which

[0127] M and R² have the abovementioned meanings,

[0128] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid-binding agent, or

[0129] β) are reacted with carbon disulphide and then with compounds ofthe formula (XII)

R²-Hal  (XII)

[0130] in which

[0131] R² has the abovementioned meaning and

[0132] Hal represents chlorine, bromine or iodine,

[0133] if appropriate in the presence of a diluent and if appropriate inthe presence of a base,

[0134] (I) that compounds of the formulae (I-1-d) to (I-5-d) shownabove, in which A, B, D, R³, X, Y and Z have the abovementionedmeanings, are obtained when compounds of the formulae (I-1-a) to (I-5-a)shown above, in which A, B, D, X, Y and Z have the abovementionedmeanings, in each case

[0135] are reacted with sulphonic acid chlorides of the formula (XIII)

R³—SO₂—Cl  (XIII)

[0136] in which

[0137] R³ has the abovementioned meaning,

[0138] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid-binding agent,

[0139] (J) that compounds of the formulae (I-1-e) to (I-5-e) shownabove, in which A, B, D, L, R⁴, R⁵, X, Y and Z have the abovementionedmeanings, are obtained when compounds of the formulae (I-1-a) to (I-4-a)shown above, in which A, B, D, X, Y and Z have the abovementionedmeanings, in each case are reacted

[0140] with phosphorus compounds of the formula (XIV)

[0141] in which

[0142] L, R⁴ and R⁵ have the abovementioned meanings and

[0143] Hal represents halogen (in particular chlorine or bromine),

[0144] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid-binding agent,

[0145] (K) that compounds of the formulae (I-1-f) to (I-5-f) shownabove, in which A, B, D, E, X, Y and Z have the abovementioned meanings,are obtained when compounds of the formulae (I-1-a) to (I-5-a), in whichA, B, D, X, Y and Z have the abovementioned meanings, in each case arereacted

[0146] with metal compounds or amines of the formulae (XV) or (XVI)

Me(OR¹⁰)_(t)  (XV)

[0147] in which

[0148] Me represents a mono- or divalent metal (preferably an alkalimetal or alkaline earth metal, such as lithium, sodium, potassium,magnesium or calcium),

[0149] t represents the number 1 or 2 and

[0150] R¹⁰, R¹¹ and R¹² independently of one another represent hydrogenor alkyl (preferably C₁-C₈-alkyl),

[0151] if appropriate in the presence of a diluent,

[0152] (L) that compounds of the formulae (I-1-g) to (I-5-g) shownabove, in which A, B, D, L, R⁶, R⁷, X, Y and Z have the abovementionedmeanings, are obtained when compounds of the formulae (I-1-a) to (I-5-a)shown above, in which A, B, D, X, Y and Z have the abovementionedmeanings, in each case

[0153] α) are reacted with isocyanates or isothiocyanates of the formula(XVII)

R⁶—N═C=L  (XVII)

[0154] in which

[0155] R⁶ and L have the abovementioned meanings,

[0156] if appropriate in the presence of a diluent and if appropriate inthe presence of a catalyst, or

[0157] β) are reacted with carbamic acid chlorides or thiocarbamic acidchlorides of the formula (XVIII)

[0158] in which

[0159] L, R⁶ and R⁷ have the abovementioned meanings,

[0160] if appropriate in the presence of a diluent and if appropriate inthe presence of an acid-binding agent.

[0161] It has furthermore been found that the new compounds of theformula (I) have a very good activity as pest control agents, preferablyas insecticides, acaricides and herbicides, and furthermore have a verygood plant tolerance, in particular with respect to crop plants.

[0162] Formula (I) provides a general definition of the compoundsaccording to the invention. Preferred substituents and ranges of theradicals shown in the formulae mentioned above and below are explainedbelow:

[0163] X preferably represents halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl,C₂-C₆-alkinyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy,cyano or nitro,

[0164] Y preferably represents hydrogen, halogen, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, cyano or nitro,

[0165] Z preferably represents halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, hydroxyl, cyano or nitro, orphenoxy, phenylthio, thiazolyloxy, pyridinyloxy, pyrimidyloxy,pyrazolyloxy, phenyl-C₁-C₄-alkyloxy or phenyl-C₁-C₄-alkylthio which arein each case optionally substituted by halogen, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, nitro or cyano,or

[0166] Y and Z, together preferably represent C₃-C₄-alkanediyl orC₃-C₄-alkenediyl which are optionally substituted by halogen,C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₄-halogenoalkyl and in which one tothree members can optionally be replaced, independently of one another,by oxygen, sulphur, nitrogen or a carbonyl group, X having one of theabovementioned meanings.

[0167] Het preferably represents one of the groups

[0168] A preferably represents hydrogen, or represents C₁-C₁₂-alkyl,C₂-C₈-alkenyl, C₁-C₁₀-alkoxy-C₁-C₈-alkyl, poly-C₁-C₈-alkoxy-C₁-C₈-alkylor C₁-C₁₀-alkylthio-C₁-C₆-alkyl which are in each case optionallysubstituted by halogen, or represents C₃-C₈-cycloalkyl which isoptionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy and inwhich one or two methylene groups are optionally replaced by oxygenand/or sulphur, or represents phenyl, naphthyl, phenyl-C₁-C₆-alkyl,naphthyl-C₁-C₆-alkyl or hetaryl having 5 or 6 ring atoms and one tothree heteroatoms from the series consisting of oxygen, sulphur andnitrogen, which are in each case optionally substituted by halogen,C₁-C₆-alkyl, C₁-C₆-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy,cyano or nitro.

[0169] B preferably represents hydrogen, C₁-C₁₂-alkyl orC₁-C₈-alkoxy-C₁-C₆-alkyl or

[0170] A, B and the carbon atom to which they are bonded preferablyrepresent C₃-C₁₀-cycloalkyl or C₅-C₁₀-cycloalkenyl, wherein onemethylene group is optionally replaced by oxygen or sulphur and whichare optionally substituted by C₁-C₈-alkyl, C₃-C₁₀-cycloalkyl,C₁-C,-halogenoalkyl, C₁-C₈-alkoxy, C₁-C₈-alkylthio, halogen or phenyl,or

[0171] A, B and the carbon atom to which they are bonded preferablyrepresent Cs-C₆-cycloalkyl which is substituted by an alkylenediyl groupwhich optionally contains one or two oxygen and/or sulphur atoms or byan alkylenedioxyl group or by an alkylenedithioyl group, thissubstituent forming a further five- to eight-membered ring with thecarbon atom to which it is bonded, or

[0172] A, B and the carbon atom to which they are bonded preferablyrepresent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl in which twosubstituents, together with the carbon atom to which they are bonded,represent C₃-C₆-alkanediyl, C₃-C₆-alkenediyl or C₄-C₆-alkanedienediylwhich are in each case optionally substituted by C₁-C₆-alkyl,C₁-C₆-alkoxy or halogen and wherein in each case one methylene group isoptionally replaced by oxygen or sulphur.

[0173] D preferably represents hydrogen, or represents C₁-C₁₂-alkyl,C₃-C₈-alkenyl, C₃-C₈-alkinyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl,poly-C₁-C₈-alkoxy-C₂-C₈-alkyl or C₁-C₁₀-alkylthio-C₂-C₈-alkyl which arein each case optionally substituted by halogen, or representsC₃-C₈-cycloalkyl which is optionally substituted by halogen,C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-halogenoalkyl and in which one or twomethylene groups which are not directly adjacent are optionally replacedby oxygen and/or sulphur, or represent phenyl, hetaryl haying 5 to 6ring atoms and one or two heteroatoms from the series consisting ofoxygen, sulphur and nitrogen, phenyl-C₁-C₆-alkyl or hetaryl-C₁-C₆-alkylhaving 5 to 6 ring atoms and one or two heteroatoms from the seriesconsisting of oxygen, sulphur and nitrogen, which are in each caseoptionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-halogenoalkyl,C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy, cyano or nitro, or

[0174] A and D together preferably represent a C₃-C₆-alkanediyl,C₃-C₆-alkenediyl or C₄-C₆-alkadienediyl group in which in each case onemethylene group is optionally replaced by oxygen or sulphur and whichare in each case optionally substituted by halogen or C₁-C₁₀-alkyl,C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₃-C₇-cycloalkyl, phenyl or benzyloxywhich are in each case optionally substituted by halogen, or by afurther C₃-C₆-alkanediyl, C₃-C₆-alkenediyl or C₄-C₆-alkadienediyl groupwhich forms a fused-on ring and in which in each case one methylenegroup is optionally replaced by oxygen or sulphur and which areoptionally substituted by C₁-C₆-alkyl, or

[0175] A and D together represent a C₃-C₆-alkanediyl or C₃-C₆-alkenediylgroup which in each case optionally contains one of the following groups

[0176] G preferably represents hydrogen (a), or represents one of thegroups

[0177] in which

[0178] E represents one metal ion equivalent or an ammonium ion,

[0179] L represents oxygen or sulphur and

[0180] M represents oxygen or sulphur.

[0181] R¹ preferably represents C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl orpoly-C₁-C₈-alkoxy-C₁-C₈-alkyl which are in each case optionallysubstituted by halogen, or represents C₃-C₈-cycloalkyl which isoptionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy and inwhich one or two methylene groups are optionally replaced by oxygenand/or sulphur,

[0182] or represents phenyl which is optionally substituted by halogen,cyano, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl,C₁-C₆-halogenoalkoxy, C₁-C₆-alkylthio or C₁-C₆-alkylsulphonyl,

[0183] or represents phenyl-C₁-C₆-alkyl which is optionally substitutedby halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkylor C₁-C₆-halogenoalkoxy,

[0184] or represents 5- or 6-membered hetaryl having one or twoheteroatoms from the series consisting of oxygen, sulphur and nitrogenwhich is optionally substituted by halogen or C₁-C₆-alkyl,

[0185] or represents phenoxy-C₁-C₆-alkyl which is optionally substitutedby halogen or C₁-C₆-alkyl or

[0186] represents 5- or 6-membered hetaryloxy-C₁-C₆-alkyl which has oneor two heteroatoms from the series consisting of oxygen, sulphur andnitrogen and is optionally substituted by halogen, amino or C₁-C₆-alkyl.

[0187] R² preferably represents C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₁-C₈-alkoxy-C₂-C₈-alkyl or poly-C₁-C₈-alkoxy-C₂-C₈-alkyl which are ineach case optionally substituted by halogen,

[0188] or represents C₃-C₈-cycloalkyl which is optionally substituted byhalogen, C₁-C₆-alkyl or C₁-C₆-alkoxy, or

[0189] represents phenyl or benzyl which are in each case optionallysubstituted by halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₆-halogenoalkyl or C₁-C₆-halogenoalkoxy.

[0190] R³ preferably represents C₁-C₈-alkyl which is optionallysubstituted by halogen, or phenyl or benzyl which are in each caseoptionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, cyano or nitro.

[0191] R⁴ and R⁵ independently of one another preferably representC₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylamino, di-(C₁-C₈-alkyl)amino,C₁-C₈-alkylthio or C₃-C₈-alkenylthio which are in each case optionallysubstituted by halogen, or represent phenyl, phenoxy or phenylthio whichare in each case optionally substituted by halogen, nitro, cyano,C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, C₁-C₄-alkylthio,C₁-C₄-halogenoalkylthio, C₁-C₄-alkyl or C₁-C₄-halogenoalkyl.

[0192] R⁶ and R⁷ independently of one another preferably representhydrogen, or represent C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy,C₃-C₈-alkenyl or C₁-C₈-alkoxy-C₂-C₈-alkyl which are in each caseoptionally substituted by halogen, or represent phenyl or benzyl whichare in each case optionally substituted by halogen, C₁-C₈-alkyl,C₁-C₈-halogenoalkyl or C₁-C₈-alkoxy, or together represent aC₃-C₆-alkylene radical which is optionally substituted by C₁-C₆-alkyland in which one methylene group is optionally replaced by oxygen orsulphur.

[0193] R¹³ preferably represents hydrogen, or C₁-C₈-alkyl orC₁-C₈-alkoxy which are in each case optionally substituted by halogen,or represents C₃-C₈-cycloalkyl which is optionally substituted byhalogen, C₁-C₄-alkyl or C₁-C₄-alkoxy and in which one methylene group isoptionally replaced by oxygen or sulphur, or represents phenyl,phenyl-C₁-C₄-alkyl or phenyl-C₁-C₄-alkoxy which are in each caseoptionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, nitro or cyano.

[0194] R¹⁴ preferably represents hydrogen or C₁-C₈-alkyl, or

[0195] R¹³ and R¹⁴ together preferably represent C₄-C₆-alkanediyl.

[0196] R¹⁵ and R¹⁶ are identical or different and preferably representC₁-C₆-alkyl, or

[0197] R¹⁵ and R¹⁶ together preferably represent a C₂-C₄-alkanediylradical which is optionally substituted by C₁-C₆-alkyl or by phenylwhich is optionally substituted by halogen, C₁-C₄-alkyl,C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, nitro or cyano.

[0198] R¹⁷ and R¹⁸ independently of one another preferably representhydrogen, or represent C₁-C₈-alkyl which is optionally substituted byhalogen, or represent phenyl which is optionally substituted by halogen,C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy,nitro or cyano, or

[0199] R¹⁷ and R⁸, together with the carbon atom to which they arebonded, represent C₅-C₇-cycloalkyl which is optionally substituted byC₁-C₄-alkyl and in which one methylene group is optionally replaced byoxygen or sulphur.

[0200] R¹⁹ and R²⁰ independently of one another preferably representC₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₁-C₁₀-alkoxy, C₁-C₁₀-alkylamino,C₃-C₁₀-alkenylamino, di-(C₁-C₁₀-alkyl)amino or di-(C₃-C₁₀-alkenyl)amino.

[0201] X particularly preferably represents fluorine, chlorine, bromine,C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl, C₁-C₂-halogenoalkoxy,cyano or nitro,

[0202] Y particularly preferably represents hydrogen, fluorine,chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, cyano or nitro,

[0203] Z particularly preferably represents fluorine, chlorine, bromine,C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl, C₁-C₂-halogenoalkoxy,hydroxy, cyano or nitro, or phenoxy or benzyloxy which are in each caseoptionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl, C₁-C₂-halogenoalkoxy, nitro or cyano,or

[0204] Y and Z, together particularly preferably representC₃-C₄-alkanediyl or C₃-C₄-alkenediyl which are optionally substituted byfluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy orC₁-C₂-halogenoalkyl and in which one or two members which are notdirectly adjacent can optionally be replaced, independently of oneanother, by oxygen, sulphur or nitrogen, X having one of theabovementioned meanings.

[0205] Het particularly preferably represents one of the groups

[0206] A particularly preferably represents hydrogen, or representsC₁-C₁₀-alkyl, C₂-C₆-alkenyl, C₁-C₈-alkoxy-C₁-C₆-alkyl,poly-C₁-C₆-alkoxy-C₁-C₆-alkyl or C₁-C₈-alkylthio-C₁-C₆-alkyl which arein each case optionally substituted by fluorine or chlorine, orrepresents C₃-C₇-cycloalkyl which is optionally substituted by fluorine,chlorine, C₁-C₄-alkyl or C₁-C₄-alkoxy and in which one or two methylenegroups are optionally replaced by oxygen and/or sulphur, or representsphenyl, furanyl, pyridyl, imidazolyl, triazolyl, pyrazolyl, indolyl,thiazolyl, thienyl or phenyl-C₁-C₄-alkyl which are in each caseoptionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl,C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, cyano or nitro.

[0207] B particularly preferably represents hydrogen, C₁-C₁₀-alkyl orC₁-C₆-alkoxy-C₁-C₄-alkyl or

[0208] A, B and the carbon atom to which they are bonded particularlypreferably represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl, wherein ineach case one methylene group is optionally replaced by oxygen orsulphur and which are optionally substituted by C₁-C₆-alkyl,C₃-C₈-cycloalkyl, C₁-C₃-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio,fluorine, chlorine or phenyl, or

[0209] A, B and the carbon atom to which they are bonded particularlypreferably represent C₅-C₆-cycloalkyl which is substituted by analkylenediyl group which optionally contains one or two oxygen orsulphur atoms or by an alkylenedioxyl group or by an alkylenedithiolgroup, this substituent, together with the carbon atom to which it isbonded, forming a further five- to seven-membered ring, or

[0210] A, B and the carbon atom to which they are bonded particularlypreferably represent C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which twosubstituents, together with the carbon atom to which they are bonded,represent C₃-C₅-alkanediyl, C₃-C₅-alkenediyl or butadienediyl which arein each case optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy,fluorine, chlorine or bromine, wherein in each case one methylene groupis optionally replaced by oxygen or sulphur.

[0211] D particularly preferably represents hydrogen, or representsC₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkinyl, C₁-C₈-alkoxy-C₂-C₆-alkyl,poly-C₁-C₆-alkoxy-C₂-C₆-alkyl or C₁-C₈-alkylthio-C₂-C₆-alkyl which arein each case optionally substituted by fluorine or chlorine, orrepresents C₃-C₇-cycloalkyl which is optionally substituted by fluorine,chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl and in whichone or two methylene groups which are not directly adjacent areoptionally replaced by oxygen and/or sulphur, or represents phenyl,furanyl, imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl,thienyl, triazolyl or phenyl-C₁-C₄-alkyl which are in each caseoptionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl,C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, cyano or nitro,or

[0212] A and D together particularly preferably represent aC₃-C₅-alkanediyl or C₃-C₅-alkenediyl group wherein in each case onecarbon atom is optionally replaced by oxygen or sulphur and which areoptionally substituted by fluorine, chlorine or by C₁-C₆-alkyl,C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, phenyl or benzyloxywhich are in each case optionally substituted by fluorine or chlorine,or

[0213] which in each case optionally contain one of the followinggroups:

[0214] G particularly preferably represents hydrogen (a), or representsone of the groups

[0215] in which

[0216] E represents one metal ion equivalent or an ammonium ion,

[0217] L represents oxygen or sulphur and

[0218] M represents oxygen or sulphur.

[0219] R¹ particularly preferably represents C₁-C₁₆-alkyl,C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkylthio-C₁-C₆-alkyl orpoly-C₁-C₆-alkoxy-C₁-C₆-alkyl which are in each case optionallysubstituted by fluorine or chlorine, or represents C₃-C₇-cycloalkylwhich is optionally substituted by fluorine, chlorine, C₁-C₅-alkyl orC₁-C₅-alkoxy and in which one or two methylene groups are optionallyreplaced by oxygen and/or sulphur,

[0220] or represents phenyl which is optionally substituted by fluorine,chlorine, bromine, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₃-halogenoalkyl, C₁-C₃-halogenoalkoxy, C₁-C₄-alkylthio orC₁-C₄-alkylsulphonyl,

[0221] or represents phenyl-C₁-C₄-alkyl which is optionally substitutedby fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₃-halogenoalkyl or C₁-C₃-halogenoalkoxy,

[0222] or represents pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanylor thienyl which are in each case optionally substituted by fluorine,chlorine, bromine or C₁-C₄-alkyl,

[0223] or represents phenoxy-C₁-C₅-alkyl which is optionally substitutedby fluorine, chlorine, bromine or C₁-C₄-alkyl, or

[0224] represents pyridyloxy-C₁-C₅-alkyl, pyrimidyloxy-C₁-C.-alkyl orthiazolyloxy-C₁-C₅-alkyl which are in each case optionally substitutedby fluorine, chlorine, bromine, amino or C₁-C₄-alkyl.

[0225] R² particularly preferably represents C₁-C₁₆-alkyl,C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl orpoly-C₁-C₆-alkoxy-C₂-C₆-alkyl which are in each case optionallysubstituted by fluorine or chlorine,

[0226] or represents C₃-C₇-cycloalkyl which is optionally substituted byfluorine, chlorine, C₁-C₄-alkyl or C₁-C₄-alkoxy, or

[0227] represents phenyl or benzyl which are in each case optionallysubstituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl,C₁-C₃-alkoxy, C₁-C₃-halogenoalkyl or C₁-C₃-halogenoalkoxy.

[0228] R³ particularly preferably represents C₁-C₆-alkyl which isoptionally substituted by fluorine or chlorine, or phenyl or benzylwhich are in each case optionally substituted by fluorine, chlorine,bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkoxy,C₁-C₂-halogenoalkyl, cyano or nitro.

[0229] R⁴ and R⁵ independently of one another particularly preferablyrepresent C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylamino,di-(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio or C₃-C₄-alkenylthio which are ineach case optionally substituted by fluorine or chlorine, or representphenyl, phenoxy or phenylthio which are in each case optionallysubstituted by fluorine, chlorine, bromine, nitro, cyano, C₁-C₃-alkoxy,C₁-C₃-halogenoalkoxy, C₁-C₃-alkylthio, C—C₃-halogenoalkylthio,C₁-C₃-alkyl or C₁-C₃-halogenoalkyl.

[0230] R⁶ and R⁷ independently of one another particularly preferablyrepresent hydrogen, or represent C₁-C₆-alkyl, C₃-C₆-cycloalkyl,C₁-C₆-alkoxy, C₃-C₆-alkenyl or C₁-C₆-alkoxy-C₂-C₆-alkyl which are ineach case optionally substituted by fluorine or chlorine, or representphenyl or benzyl which are in each case optionally substituted byfluorine, chlorine, bromine, C₁-C₅-halogenoalkyl, C₁-C₅-alkyl orC₁-C₅-alkoxy, or together represent a C₃-C₆-alkylene radical which isoptionally substituted by C₁-C₄-alkyl and in which one methylene groupis optionally replaced by oxygen or sulphur.

[0231] R¹³ particularly preferably represents hydrogen, or C₁-C₆-alkylor C₁-C₆-alkoxy which are in each case optionally substituted byfluorine or chlorine, or represents C₃-C₇-cycloalkyl which is optionallysubstituted by fluorine, C₁-C₂-alkyl or C₁-C₂-alkoxy and in which onemethylene group is optionally replaced by oxygen or sulphur, orrepresents phenyl, phenyl-C₁-C₃-alkyl or phenyl-C₁-C₂-alkyloxy which arein each case optionally substituted by fluorine, chlorine, bromine,C₁-C₅-alkyl, C₁-C₅-alkoxy, C₁-C₂-halogenoalkyl, C₁-C₂-halogenoalkoxy,nitro or cyano.

[0232] R¹⁴ particularly preferably represents hydrogen or C₁-C₆-alkyl,or

[0233] R¹³ and R¹⁴ together particularly preferably representC₄-C₆-alkanediyl.

[0234] R¹⁵ and R¹⁶ are identical or different and particularlypreferably represent C₁-C₄-alkyl, or

[0235] R¹⁵ and R¹⁶ together particularly preferably represent aC₂-C₃-alkanediyl radical which is optionally substituted by C₁-C₄-alkylor by phenyl which is optionally substituted by fluorine, chlorine,bromine, C₁-C₂-alkyl, C₁-C₂-halogenoalkyl, C₁-C₂-alkoxy,C₁-C₂-halogenoalkoxy, nitro or cyano.

[0236] X especially preferably represents fluorine, chlorine, bromine,methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tert-butyl,methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl,trifluoromethoxy, difluoromethoxy, cyano or nitro,

[0237] Y especially preferably represents hydrogen, fluorine, chlorine,bromine, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl,tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl,trifluoromethoxy, difluoromethoxy, cyano or nitro,

[0238] Z especially preferably represents fluorine, chlorine, bromine,methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tert-butyl,methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl,trifluoromethoxy, difluoromethoxy, cyano or nitro, or

[0239] Y and Z, together especially preferably representC₃-C₄-alkanediyl which is optionally substituted by fluorine, chlorine,methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, iso-propoxyor trifluoromethyl and in which two members which are not directlyadjacent are optionally replaced by oxygen, X having one of theabovementioned meanings.

[0240] Het especially preferably represents one of the groups

[0241] A especially preferably represents hydrogen, or representsC₁-C₈-alkyl, C₂-C₄-alkenyl, C₁-C₆-alkoxy-C₁-C₄-alkyl,poly-C₁-C₄-alkoxy-C₁-C₄-alkyl or C₁-C₆-alkylthio-C₁-C₄-alkyl which arein each case optionally substituted by fluorine or chlorine, orrepresents C₃-C₆-cycloalkyl which is optionally substituted by fluorine,chlorine, methyl or methoxy and in which one or two methylene groups areoptionally replaced by oxygen and/or sulphur, or represents phenyl,pyridyl or benzyl which are in each case optionally substituted byfluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl,methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro.

[0242] B especially preferably represents hydrogen, C₁-C₈-alkyl orC₁-C₄-alkoxy-C₁-C₂-alkyl or

[0243] A, B and the carbon atom to which they are bonded especiallypreferably represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl, wherein ineach case one methylene group is optionally replaced by oxygen orsulphur and which are optionally substituted by methyl, ethyl, n-propyl,iso-propyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl,trifluoromethyl, methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy,iso-butoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, fluorine,chlorine or phenyl, or

[0244] A, B and the carbon atom to which they are bonded especiallypreferably represent C₅-C₆-cycloalkyl which is substituted by analkylenediyl group which optionally contains an oxygen or sulphur atomor by an alkylenedioxyl group, this substituent forming a further five-or six-membered ring with the carbon atom to which it is bonded, or

[0245] A, B and the carbon atom to which they are bonded especiallypreferably represent C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which twosubstituents, together with the carbon atoms to which they are bonded,represent C₃-C₄-alkanediyl, C₃-C₄-alkenediyl or butadienediyl, whereinin each case one methylene group is optionally replaced by oxygen orsulphur.

[0246] D especially preferably represents hydrogen, or representsC₁-C₈-alkyl, C₃-C₄-alkenyl, C₃-C₄-alkinyl, C₁-C₆-alkoxy-C₂-C₄-alkyl,poly-C₁-C₄-alkoxy-C₂-C₄-alkyl, C₁-C₄-alkylthio-C₂-C₄-alkyl orC₃-C₆-cycloalkyl which are in each case optionally substituted byfluorine or chlorine and in which one or two methylene groups which arenot directly adjacent are optionally replaced by oxygen and/or sulphur,or represent phenyl, furanyl, pyridyl, thienyl or benzyl which are ineach case optionally substituted by fluorine, chlorine, bromine, methyl,ethyl, n-propyl, iso-propyl, methoxy, ethoxy, trifluoromethyl,trifluoromethoxy, cyano or nitro, or

[0247] A and D together especially preferably represent aC₃-C.-alkanediyl or C₃-C₅-alkenediyl group wherein in each case onemethylene group is optionally replaced by oxygen or sulphur and whichare optionally substituted by fluorine, chlorine or by C₁-C₆-alkyl,C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, phenyl or benzyloxywhich are in each case optionally substituted by fluorine or chlorine.

[0248] G especially preferably represents hydrogen (a), or representsone of the groups

[0249] in which

[0250] E represents one metal ion equivalent or an ammonium ion,

[0251] L represents oxygen or sulphur and

[0252] M represents oxygen or sulphur.

[0253] R¹ especially preferably represents C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl,C₁-C₄-alkoxy-C₁-C₆-alkyl, C₁-C₄-alkylthio-C₁-C₆-alkyl orpoly-C₁-C₄-alkoxy-C₁-C₄-alkyl which are in each case optionallysubstituted by fluorine or chlorine, or represents C₃-C₆-cycloalkylwhich is optionally substituted by fluorine, chlorine, methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, methoxy, ethoxy,n-propoxy or iso-propoxy and in which one or two methylene groups areoptionally replaced by oxygen and/or sulphur,

[0254] or represents phenyl which is optionally substituted by fluorine,chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl,methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio,ethylthio, methylsulphonyl or ethylsulphonyl,

[0255] or represents benzyl which is optionally substituted by fluorine,chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy,trifluoromethyl or trifluoromethoxy,

[0256] or represents furanyl, thienyl or pyridyl which are in each caseoptionally substituted by fluorine, chlorine, bromine, methyl or ethyl,

[0257] or represents phenoxy-C₁-C₄-alkyl which is optionally substitutedby fluorine, chlorine, methyl or ethyl, or representspyridyloxy-C₁-C₄-alkyl, pyrimidyloxy-C₁-C₄-alkyl orthiazolyloxy-C₁-C₄-alkyl which are in each case optionally substitutedby fluorine, chlorine, amino, methyl or ethyl.

[0258] R² especially preferably represents C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl,C₁-C₄-alkoxy-C₂-C₆-alkyl or poly-C₁-C₄-alkoxy-C₂-C₆-alkyl which are ineach case optionally substituted by fluorine or chlorine,

[0259] or represents C₃-C₆-cycloalkyl which is optionally substituted byfluorine, chlorine, methyl, ethyl, n-propyl, iso-propyl or methoxy,

[0260] or represents phenyl or benzyl which are in each case optionallysubstituted by fluorine, chlorine, cyano, nitro, methyl, ethyl,n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl ortrifluoromethoxy.

[0261] R³ especially preferably represents methyl, ethyl, propyl,iso-prpyl, butyl or tert-butyl which are optionally substituted byfluorine or chlorine, or phenyl or benzyl which are in each caseoptionally substituted by fluorine, chlorine, bromine, methyl, ethyl,iso-propyl, tert-butyl, methoxy, ethoxy, iso-propoxy, trifluoromethyl,trifluoromethoxy, cyano or nitro.

[0262] R⁴ and R⁵ independently of one another especially preferablyrepresent C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino,di-(C₁-C₄-alkyl)amino or C₁-C₄-alkylthio which are in each caseoptionally substituted by fluorine or chlorine, or represent phenyl,phenoxy or phenylthio which are in each case optionally substituted byfluorine, chlorine, bromine, nitro, cyano, methyl, methoxy,trifluoromethyl or trifluoromethoxy.

[0263] R⁶ and R⁷ independently of one another especially preferablyrepresent hydrogen, or represent C₁-C₄-alkyl, C₃-C₆-cycloalkyl,C₁-C₄-alkoxy, C₃-C₄-alkenyl or C₁-C₄-alkoxy-C₂-C₄-alkyl which are ineach case optionally substituted by fluorine or chlorine, or representphenyl or benzyl which are in each case optionally substituted byfluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl, ortogether represent a C₅-C₆-alkylene radical which is optionallysubstituted by methyl or ethyl and in which one methylene group isoptionally replaced by oxygen or sulphur.

[0264] The abovementioned general definitions of radicals andexplanations or those given in preferred ranges can be combined with oneanother as desired, that is to say also between the particular rangesand preferred ranges. They apply accordingly to the end products and tothe precursors and intermediate products.

[0265] The compounds of the formula (I) in which a combination of themeanings given above as preferred (preferably) is present are preferredaccording to the invention.

[0266] The compounds of the formula (I) in which a combination of themeanings given above as particularly preferred is present areparticularly preferred according to the invention.

[0267] The compounds of the formula (I) in which a combination of themeanings given above as especially preferred is present are especiallypreferred according to the invention.

[0268] Saturated or unsaturated hydrocarbon radicals such as alkyl oralkenyl, also in combination with heteroatoms, such as, for example, inalkoxy, can in each case be straight-chain or branched where possible.

[0269] Optionally substituted radicals can be mono- or polysubstituted,and the substituents can be identical or different in the case ofpolysubstitutions.

[0270] The following compounds of the formula (I-1-a) may be mentionedspecifically, in addition to the compounds mentioned in the preparationexamples: TABLE 1

A B CH₃ H C₂H₅ H C₃H₇ H i-C₃H₇ H C₄H₉ H i-C₄H₉ H s-C₄H₉ H t-C₄H₉ H CH₃CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉ CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂O—(CH₂)₂——(CH₂)₂S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂——(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂— —(CH₂)₂—CHi-C₃H₇—(CH₂)₂——(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂— —(CH₂)₂—CHOC₃H₇—(CH₂)₂——(CH₂)₂—CHiO-C₃H₇—(CH₂)₂— —CH₂—(CHCH₃)₂—(CH₂)₂—

[0271] Table 2: A and B have the same meaning as in Table 1, with X=CH₃;Y=Cl; Z=CH₃

[0272] Table 3: A and B have the same meaning as in Table 1, with X=Cl;Y=Cl; Z=Cl

[0273] The following compounds of the formula (I-2-a) may be mentionedspecifically in addition to the compounds mentioned in the preparationexamples: TABLE 4

A B CH₃ H C₂H₅ H i-C₃H₇ H C₄H₉ H i-C₄H₉ H s-C₄H₉ H t-C₄H₉ H CH₃ CH₃ C₂H₅CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉ CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉ CH₃ C₂H₅C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₆— —CH₂—CHCH₃—(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂——(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂— —(CH₂)₂—CHI—C₃H₇—(CH₂)₂——(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂— —(CH₂)₂—CHOC₃H₇—(CH₂)₂——(CH₂)₂—CHiO—C₃H₇—(CH₂)₂— —CH₂—(CHCH₃)₂—(CH₂)₂—

[0274] Table 5: A and B have the same meaning as in Table 4, with X=CH₃;Y=Cl; Z=CH₃

[0275] Table 6: A and B have the same meaning as in Table 4, with X=Cl;Y=Cl; Z=Cl

[0276] The following compounds of the formula (I-3-a) may be mentionedspecifically in addition to the compounds mentioned in the preparationexamples: TABLE 7

A B CH₃ H C₂H₅ H C₃H₇ H i-C₃H₇ H C₄H₉ H i-C₄H₉ H s-C₄H₉ H t-C₄H₉ H CH₃CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉ CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂—O—(CH₂)₂——(CH₂)₂—S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂——(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂— —(CH₂)₂—CHi—C₃H₇—(CH₂)₂——(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂— —(CH₂)₂—CHiO—C₃H₇—(CH₂)₂——CH₂—(CHCH₃)₂—(CH₂)₂—

[0277] Table 8: A and B have the same meaning as in Table 7, with X=CH₃;Y=Cl; Z=CH₃

[0278] Table 9: A and B have the same meaning as in Table 7, with X=Cl;Y=Cl; Z=Cl

[0279] The following compounds of the formula (I-4-a) may be mentionedspecifically in addition to the compounds mentioned in the preparationexamples: TABLE 10

A D H CH₃ H C(CH₃)₃ H C(CH₃)₂CH₂Cl CH₃ CH₃ CH₃ CH₂CHCH₃CH₂CH₃ HCH═C(CH₃)₂ CH₃

CH₃

CH₃

CH₃

CH₃

CH₃ CH₃

CH₃

CH₃

CH₃

H

CH₃ C₅H₉ CH₃ C₃H₅ H C₃H₄Cl (CH₂)₃ (CH₂)₄ C(CH₃)₂OC(CH₃)₂

[0280] Table 11: A and D have the same meaning as in Table 10, withX=CH₃; Y=Cl; Z=CH₃

[0281] Table 12: A and D have the same meaning as in Table 10, withX=Cl; Y=Cl; Z=Cl

[0282] The following compounds of the formula (I-5-a) may be mentionedspecifically in addition to the compounds mentioned in the preparationexamples: TABLE 3

A CH₃ CH(CH₃)₂

[0283] Table 14: A has the same meaning as in Table 13, with X=CH₃—Y=Cl;Z=CH₃

[0284] Table 15: A has the same meaning as in Table 13, with X=Cl; Y=Cl;Z=Cl

[0285] If ethylN-[(4,5-dichloro-2-methyl)-phenylacetyl]-1-amino-4-ethyl-cyclohexanecarboxylateis used as the starting substance according to process (A), the courseof the process according to the invention can be represented by thefollowing equation:

[0286] If ethyl O-[(2,5-dichloro-4-methyl)-phenylacetyl]-hydroxyacetateis used according to process (B), the course of the process according tothe invention can be represented by the following equation:

[0287] If ethyl2-[(2-chloro-4,5-dimethyl)-phenyl]-4-(4-methoxy)-benzylmercapto-4-methyl-3-oxo-valerateis used according to process (C), the course of the process according tothe invention can be represented by the following equation:

[0288] If, for example,(chlorocarbonyl)-2-[(4,5-dichloro-2-methyl)-phenyl]-ketene and acetoneare used as starting compounds according to process (D), the course ofthe process according to the invention can be represented by thefollowing equation:

[0289] If, for example,(chlorocarbonyl)-2-[(2,4,5-trimethyl)-phenyl]-ketene and thiobenzamideare used as starting compounds according to process (E), the course ofthe process according to the invention can be represented by thefollowing equation:

[0290] If3-[(2,5-dichloro-4-methyl)-phenyl]-5,5-dimethyl-pyrrolidine-2,4-di oneand pivaloyl chloride are used as starting substances according toprocess (Fα), the course of the process according to the invention canbe represented by the following equation:

[0291] If3-[(2,4,5-trichloro)-phenyl]-4-hydroxy-5-phenyl-Δ³-dihydrofuran-2-oneand acetic anhydride are used as starting compounds according to process(F) (variant β), the course of the process according to the inventioncan be represented by the following equation:

[0292] If8-[(2,4-dichloro-5-methyl)-phenyl]-5,5-pentamethylene-pyrrolidine-2,4-dioneand ethoxyethyl chloroformate are used as starting compounds accordingto process (G), the course of the process according to the invention canbe represented by the following equation:

[0293] If3-[(2-bromo-4,5-dimethyl)-phenyl]-4-hydroxy-6-(3-pyridyl)-pyrone andmethyl chloromonothioformate are used as starting substances accordingto process (H) (variant α), the course of the reaction can berepresented as follows:

[0294] If5-[(5-chloro-2-fluoro-4-methyl)-phenyl]-6-hydroxy-2-(4-chlorophenyl)-thiazin-4-one,carbon disulphide and methyl iodide are used as starting componentsaccording to process (H) (variant β), the course of the reaction can berepresented as follows:

[0295] If2-[(2,4,5-trimethyl)-phenyl]-5,5-[(3-methyl)-pentamethylene]-pyrrolidine-2,4-dioneand methanesulphonyl chloride are used as starting substances accordingto process (I), the course of the reaction can be represented by thefollowing equation:

[0296] If2-[(2-chloro-4,5-dimethyl)-phenyl]-4-hydroxy-5-methyl-6-(2-pyridyl)-pyroneand methanethio-phosphonic acid chloride 2,2,2-trifluoroethyl ester areused as starting substances according to process (J), the course of thereaction can be represented by the following equation:

[0297] If3-[(2,4,5-trichloro)-phenyl]-5-cyclopropyl-5-methyl-pyrrolidine-2,4-dione and NaOH are used as components according to process (K), the courseof the process according to the invention can be represented by thefollowing equation:

[0298] If3-[(2-chloro-4-bromo-5-methyl)-phenyl]-4-hydroxy-5,5-tetramethylene-Δ³-dihydro-furan-2-oneand ethyl isocyanate are used as starting substances according toprocess (L) (variant α), the course of the reaction can be representedby the following equation:

[0299] If3-[(2-chloro-4,5-dimethyl)-phenyl]-5-methyl-pyrrolidine-2,4-dione anddimethylcarbamoyl chloride are used as starting substances according toprocess (L) (variant β), the course of the reaction can be representedby the following equation:

[0300] The compounds of the formula (II)

[0301] in which

[0302] A, B, X, Y, Z and R⁸ have the abovementioned meanings,

[0303] required as starting substances in process (A) according to theinvention are new.

[0304] The acylamino acid esters of the formula (II) are obtained, forexample, when amino acid derivatives of the formula (XIX)

[0305] in which

[0306] A, B and R⁸ have the abovementioned meanings,

[0307] are acylated with substituted phenylacetic acid halides of theformula (XX)

[0308] in which

[0309] X, Y and Z have the abovementioned meanings and

[0310] Hal represents chlorine or bromine

[0311] (Chem. Reviews 52 237-416 (1953); Bhattacharya, Indian J. Chem.6, 341-5, 1968)

[0312] or when acylamino acids of the formula (XXI)

[0313] in which

[0314] A, B, X, Y and Z have the abovementioned meanings,

[0315] are esterified (Chem. Ind. (London) 1568 (1968)).

[0316] The compounds of the formula (XXI)

[0317] in which

[0318] A, B, X, Y and Z have the abovementioned meanings,

[0319] are new.

[0320] The compounds of the formula (XXI) are obtained when amino acidsof the formula (XXII)

[0321] in which

[0322] A and B have the abovementioned meanings,

[0323] are acylated with substituted phenylacetic acid halides of theformula (XX)

[0324] in which

[0325] X, Y and Z have the abovementioned meanings and

[0326] Hal represents chlorine or bromine,

[0327] in a Schotten-Baumann reaction (Organikum, VEB Deutscher Verlagder Wissenschaften, Berlin 1977, page 505).

[0328] The compounds of the formula (XX) are new in some cases and theycan be prepared by known processes.

[0329] The compounds of the formula (XX) are obtained, for example, by aprocedure in which substituted phenylacetic acids of the formula (XXIII)

[0330] in which

[0331] X, Y and Z have the abovementioned meaning,

[0332] are reacted with halogenating agents (for example thionylchloride, thionyl bromide, oxalyl chloride, phosgene, phosphorustrichloride, phosphorus tribromide or phosphorus pentachloride), ifappropriate in the presence of a diluent (for example optionallychlorinated aliphatic or aromatic hydrocarbons, such as toluene ormethylene chloride), at temperatures from −20° C. to 150° C., preferablyfrom −10° C. to 100° C.

[0333] The compounds of the formula (XXIII) are new in some cases, andthey can be preapred by processes known from the literature (Organikum15th edition, page 533, VEB Deutscher Verlag der Wissenschaften, Berlin1977). The compounds of the formula (XXIII) are obtained, for example,by a procedure in which substituted phenylacetic acid esters of theformula (XXIV)

[0334] in which

[0335] X, Y, Z and R⁸ have the abovementioned meaning,

[0336] are hydrolysed in the presence of an acid (for example aninorganic acid, such as hydrochloric acid) or a base (for example analkali metal hydroxide, such as sodium hydroxide or potassium hydroxide)and if appropriate a diluent (for example an aqueous alcohol, such asmethanol or ethanol) at temperatures between 0° C. and 150° C.,preferably between 20° C. and 100° C.

[0337] The compounds of the formula (XXIV) are new in some cases andthey can be prepared by processes which are known in principle.

[0338] The compounds of the formula (XXIV) are obtained, for example, bya procedure in which substituted 1,1,1-trichloro-2-phenylethanes of theformula (XXV)

[0339] in which

[0340] X, Y and Z have the abovementioned meaning,

[0341] are reacted first with alcoholates (for example alkali metalalcoholates, such as sodium methylate or sodium ethylate) in thepresence of a diluent (for example the alcohol derived from thealcoholate) at temperatures between 0° C. and 150° C., preferablybetween 20° C. and 120° C., and then with an acid (preferably aninorganic acid, such as, for example, sulphuric acid) at temperaturesbetween −20° C. and 150° C., preferably 0° C. and 100° C. (cf DE 3 314249).

[0342] The compounds of the formula (XXV) are new in some cases and theycan be prepared by processes which are known in principle.

[0343] The compounds of the formula (XXV) are obtained, for example,when anilines of the formula (XXVI)

[0344] in which

[0345] X, Y and Z have the abovementioned meaning,

[0346] are reacted with vinylidene chloride (CH₂═CCl₂) in the presenceof an alkyl nitrite of the formula (XXVII)

R²¹—ONO  (XXVII)

[0347] in which

[0348] R²¹ represents alkyl, preferably C₁-C₆-alkyl,

[0349] in the presence of copper(II) chloride and if appropriate in thepresence of a diluent (for example an aliphatic nitrite, such asacetonitrile), at a temperature of −20° C. to 80° C., preferably 0° C.to 60° C.

[0350] The compounds of the formula (XXVI) and (XXVII) are knowncompounds of organic chemistry. Copper(II) chloride and vinylidenechloride have been known and commercially obtainable for a long time.

[0351] The compounds of the formula (XIX) and (XXII) are known in somecases and/or they can be prepared by known processes (see, for example,Compagnon, Miocque Ann. Chim. (Paris) [14] 5, pages 11-22, 23-27(1970)).

[0352] The substituted cyclic aminocarboxylic acids of the formula(XXIIa) in which A and B form a ring are in general obtainable by theBucherer-Bergs synthesis or by the Strecker synthesis and are in eachcase obtained in these syntheses in different isomer forms. Thus, underthe conditions of the Bucherer-Bergs synthesis, the isomers (forsimplicity called β below) in which the radicals R and the carboxylgroup are equatorial are predominantly obtained, while under theconditions of the Strecker synthesis the isomers (for simplicity calleda below) in which the amino group and the radicals R are equatorial arepredominantly obtained.

[0353] (L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C.Jitrangeri, Can. J. Chem. 53, 3339 (1975)).

[0354] Furthermore, the starting substances of the formula (II)

[0355] in which

[0356] A, B, X, Y, Z and Rx have the abovementioned meanings,

[0357] used in the above process (A) can be prepared when aminonitrilesof the formula

[0358] in which

[0359] A and B have the abovementioned meanings,

[0360] are reacted with substituted phenylacetic acid halides of theformula (X

[0361] in which

[0362] X, Y, Z and H have the abovementioned meanings,

[0363] to give compounds of the formula (XXIX)

[0364] in which

[0365] A, B, X, Y and Z have the abovementioned meanings,

[0366] and these are then subjected to acid alcoholysis.

[0367] The compounds of the formula (XXIX) are likewise new.

[0368] The compounds of the formula (III)

[0369] in which

[0370] A, B, X, Y, Z and R⁸ have the abovementioned meanings,

[0371] required as starting substances in process (B) according to theinvention are new.

[0372] They can be prepared in a simple manner by methods which areknown in principle.

[0373] The compounds of the formula (III) are obtained, for example,when

[0374] 2-hydroxycarboxylic acid esters of the formula (XXX)

[0375] in which

[0376] A, B and R⁸ have the abovementioned meanings,

[0377] are acylated with substituted phenylacetic acid halides of theformula (XX)

[0378] in which

[0379] X, Y, Z and Hal have the abovementioned meanings

[0380] (Chem. Reviews 52, 237-416 (1953)).

[0381] Compounds of the formula (III) are furthermore obtained whensubstituted phenylacetic acids of the formula (XXII)

[0382] in which

[0383] X, Y and Z have the abovementioned meanings,

[0384] are alkylated with α-halogenocarboxylic acid esters of theformula (XXXI)

[0385] in which

[0386] A, B and R⁸ have the abovementioned meanings and

[0387] Hal represents chlorine or bromine.

[0388] The compounds of the formula (XXXI) are commercially obtainable.

[0389] The compounds of the formula (IV)

[0390] in which

[0391] A, B, W, X, Y, Z and R⁸ have the abovementioned meanings,

[0392] required as starting substances in the above process (C) are new.

[0393] They can be prepared by methods which are known in principle.

[0394] The compounds of the formula (IV) are obtained, for example, whensubstituted phenylacetic acid esters of the formula (XXIV)

[0395] in which

[0396] X, Y, R⁸ and Z have the abovementioned meanings,

[0397] are acylated with 2-benzylthio-carboxylic acid halides of theformula (XXXII)

[0398] in which

[0399] A, B and W have the abovementioned meanings and

[0400] Hal represents halogen (in particular chlorine or bromine),

[0401] in the presence of strong bases (see, for example, M. S.Chambers, E. J. Thomas, D. J. Williams, J. Chem. Soc. Chem. Commun.,(1987), 1228).

[0402] The benzylthio-carboxylic acid halides of the formula (XXXII) areknown in some cases and/or they can be prepared by known processes (J.Antibiotics (1983), 26, 1589).

[0403] The halogenocarbonylketenes of the formula (VI) required asstarting substances in process (D) are new. They can be prepared in asimple manner by methods which are known in principle (cf., for example,Org. Prep. Proced. Int., 7, (4), 155-158, 1975 and DE 1 945 703). Thecompounds of the formula (VI)

[0404] in which

[0405] X, Y and Z have the abovementioned meanings and

[0406] Hal represents chlorine or bromine,

[0407] are obtained when

[0408] substituted phenylmalonic acids of the formula (XXXIII)

[0409] in which

[0410] X, Y and Z have the abovementioned meanings,

[0411] are reacted with acid halides, such as, for example, thionylchloride, phosphorus(V) chloride, phosphorus(III) chloride, oxalylchloride, phosgene or thionyl bromide, if appropriate in the presence ofcatalysts, such as, for example, diethylformamide,methyl-stearylformamide or triphenylphosphine, and if appropriate in thepresence of bases, such as, for example, pyridine or triethylamine, at atemperature between −20° C. and 200° C., preferably between 0° C. and150° C.

[0412] The substituted phenylmalonic acids of the formula (X III) arenew. However, they can be prepared in a simple manner by known processes(cf., for example, Organikum, VEB Deutscher Verlag der Wissenschaften,Berlin 1977, page 517 et seq.), for example from substitutedphenylmalonic acid esters of the formula (XXXIV)

[0413] in which

[0414] X, Y, Z and R⁸ have the abovementioned meaning,

[0415] by hydrolysis.

[0416] The carbonyl compounds of the formula (V) or silylenol ethersthereof of the formula (Va)

[0417] in which

[0418] A, D and R^(8′) have the abovementioned meanings,

[0419] required as starting substances for process (E) according to theinvention are commercially obtainable compounds which are generallyknown or accessible by known processes.

[0420] The preparation of the ketene acid chlorides of the formula (VI)required as starting substances for carrying out process (E) accordingto the invention has already been described in the case of process (D)according to the invention. The thioamides of the formula (VII)

[0421] in which

[0422] A has the abovementioned meaning,

[0423] required for carrying out process (E) according to the inventionare compounds which are generally known in organic chemistry.

[0424] The malonic acid esters of the formula (XXXIV)

[0425] in which

[0426] R⁸, X, Y and Z have the abovementioned meanings,

[0427] are new and can be prepared by generally known methods of organicchemistry (cf., for example, Tetrahedron Lett. 27, 2763(1986) andOrganikum VEB Deutscher Verlag der Wissenschaften, Berlin 1977, page 587et seq.).

[0428] The acid halides of the formula (VIII), carboxylic acidanhydrides of the formula (IX), chloroformic acid esters or chloroformicacid thioesters of the formula (X), chloromonothioformic acid esters orchlorodithioformic acid esters of the formula (XI), alkyl halides of theformula (XII), sulphonic acid chlorides of the formula (XIII),phosphorus compounds of the formula (XIV) and metal hydroxides, metalalkoxides or amines of the formula (XV) and (XVI) and isocyanates of theformula (XVII) and carbamic acid chlorides of the formula (XVIII)furthermore required as starting substances for carrying out processes(F), (G), (H), (I), (J), (K) and (L) according to the invention aregenerally known compounds of organic or inorganic chemistry.

[0429] The compounds of the formulae (V), (VII) to (XVIII), (XIX),(XMI), (XXVIII), (XXX), (XXXI), (XXII), (XXXIII) and (X V) arefurthermore known from the patent applications cited above and/or can beprepared by the methods mentioned therein.

[0430] Process (A) is characterized in that compounds of the formula(II) in which A, B, X, Y, Z and R⁸ have the abovementioned meanings aresubjected to intramolecular condensation in the presence of a diluentand in the presence of a base.

[0431] Diluents which can be employed in process (A) according to theinvention are all the organic solvents which are inert towards thereaction participants. Solvents which can preferably be used arehydrocarbons, such as toluene and xylene, and furthermore ethers, suchas dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether anddiglycol dimethyl ether, and also polar solvents, such as dimethylsulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone, aswell as alcohols, such as methanol, ethanol, propanol, iso-propanol,butanol, iso-butanol and tert-butanol.

[0432] All the customary proton acceptors can be employed as the base(deprotonating agent) in carrying out process (A) according to theinvention. Proton acceptors which can preferably be used are alkalimetal and alkaline earth metal oxides, hydroxides and carbonates, suchas sodium hydroxide, potassium hydroxide, magnesium oxide, calciumoxide, sodium carbonate, potassium carbonate and calcium carbonate,which can also be employed in the presence of phase transfer catalysts,such as, for example, triethylbenzylammonium chloride,tetrabutylammonium bromide, Adogen 464 (=methyltrialkyl(C₈-C₁₀)ammoniumchloride) or TDA 1 (=tris-(methoxyethoxyethyl)-amine). Alkali metals,such as sodium or potassium, can moreover be used. Alkali metal andalkaline earth metal amides and hydrides, such as sodium amide, sodiumhydride and calcium hydride, and in addition also alkali metalalcoholates, such as sodium methylate, sodium ethylate and potassiumtert-butylate, can furthermore be employed.

[0433] The reaction temperature can be varied within a substantial rangewhen carrying out process (A) according to the invention. The reactionis in general carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

[0434] Process (A) according to the invention is in general carried outunder normal pressure.

[0435] In carrying out process (A) according to the invention, thereaction component of the formula (II) and the deprotonating base are ingeneral employed in equimolar to about twice the equimolar amounts.However, it is also possible to use one or other of the components in alarger excess (up to 3 mol).

[0436] Process (B) is characterized in that compounds of the formula(III) in which A, B, X, Y, Z and R⁸ have the abovementioned meanings aresubjected to intramolecular condensation in the presence of a diluentand in the presence of a base.

[0437] Diluents which can be employed in process (B) according to theinvention are all the organic solvents which are inert towards thereaction participants. Solvents which can preferably be used arehydrocarbons, such as toluene and xylene, and furthermore ethers, suchas dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether anddiglycol dimethyl ether, and also polar solvents, such as dimethylsulphoxide, sulpholane, dimethylformamide and N-methyl-pyrrolidone.Alcohols, such as methanol, ethanol, propanol, iso-propanol, butanol,iso-butanol and tert-butanol, can furthermore be employed.

[0438] All the customary proton acceptors can be employed as the base(deprotonating agent) in carrying out process (B) according to theinvention. Proton acceptors which can preferably be used are alkalimetal and alkaline earth metal oxides, hydroxides and carbonates, suchas sodium hydroxide, potassium hydroxide, magnesium oxide, calciumoxide, sodium carbonate, potassium carbonate and calcium carbonate,which can also be employed in the presence of phase transfer catalysts,such as, for example, triethylbenzylammonium chloride,tetrabutylammonium bromide, Adogen 464 (=methyltrialkyl(C₈-C₁₀)ammoniumchloride) or TDA 1 (=tris-(methoxyethoxyethyl)-amine). Alkali metals,such as sodium or potassium, can moreover be used. Alkali metal andalkaline earth metal amides and hydrides, such as sodium amide, sodiumhydride and calcium hydride, and in addition also alkali metalalcoholates, such as sodium methylate, sodium ethylate and potassiumtert-butylate, can furthermore be employed.

[0439] The reaction temperature can be varied within a substantial rangewhen carrying out process (B) according to the invention. The reactionis in general carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

[0440] Process (B) according to the invention is in general carried outunder normal pressure.

[0441] In carrying out process (B) according to the invention, thereaction components of the formula (III) and the deprotonating bases arein general employed in approximately equimolar amounts. However, it isalso possible to use one or other of the components in a larger excess(up to 3 mol).

[0442] Process (C) is characterized in that compounds of the formula(IV) in which A, B, W, X, Y, Z and R⁸ have the abovementioned meaningare subjected to intramolecular cyclization in the presence of an acidand if appropriate in the presence of a diluent.

[0443] Diluents which can be employed in process (C) according to theinvention are all the organic solvents which are inert towards thereaction participants. Solvents which can preferably be used arehydrocarbons, such as toluene and xylene, and furthermore halogenatedhydrocarbons, such as methylene chloride, chloroform, ethylene chloride,chlorobenzene and dichlorobenzene, and also polar solvents, such asdimethyl sulphoxide, sulpholane, dimethylformamide andN-methylpyrrolidone. Alcohols, such as methanol, ethanol, propanol,iso-propanol, butanol, iso-butanol and tert-butanol, can furthermore beemployed.

[0444] If appropriate, the acid employed can also serve as the diluent.

[0445] Acids which can be employed in process (C) according to theinvention are all the customary inorganic and organic acids, such as,for example, hydrogen halide acids, sulphuric acid and alkyl-, aryl- andhaloalkylsulphonic acids, and halogenated alkylcarboxylic acids, suchas, for example, trifluoroacetic acid, are used in particular.

[0446] The reaction temperature can be varied within a substantial rangein carrying out process (C) according to the invention. The reaction isin general carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

[0447] Process (C) according to the invention is in general carried outunder normal pressure.

[0448] In carrying out process (C) according to the invention, thereaction components of the formula (IV) and the acid are employed, forexample, in equimolar amounts. Where appropriate, however, it is alsopossible to employ the acid in catalytic amounts.

[0449] Process (D) according to the invention is characterized in thatcarbonyl compounds of the formula (V) or silylenol ethers thereof of theformula (Va) are reacted with ketene acid halides of the formula (VI),if appropriate in the presence of a diluent and if appropriate in thepresence of an acid acceptor.

[0450] Diluents which can be employed in process (D) according to theinvention are all the organic solvents which are inert towards thereaction participants. Solvents which can preferably be used arehydrocarbons, such as o-dichlorobenzene, tetralin, toluene and xylene,and furthermore ethers, such as dibutyl ether, glycol dimethyl ether anddiglycol dimethyl ether, and also polar solvents, such as dimethylsulphoxide, sulpholane, dimethylformamide or N-methyl-pyrrolidone.

[0451] All the customary acid acceptors can be used as acid acceptors incarrying out process (D) according to the invention.

[0452] Acid acceptors which can preferably be used are tertiary amines,such as triethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base orN,N-dimethyl-aniline.

[0453] The reaction temperature can be varied within a substantial rangein carrying out process (D) according to the invention. The reaction isexpediently carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 220° C.

[0454] Process (D) according to the invention is preferably carried outunder normal pressure.

[0455] In carrying out process (D) according to the invention, thereaction components of the formulae (V) and (VI) and if appropriate theacid acceptor are in general employed in approximately equimolaramounts. However, it is also possible to use one or other of thecomponents in a larger excess (up to 5 mol).

[0456] Process (E) according to the invention is characterized in thatthioamides of the formula (VIII) are reacted with ketene acid halides ofthe formula (VI), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid acceptor.

[0457] Diluents which can be employed in process variant (E) accordingto the invention are all the inert organic solvents. Solvents which canpreferably be used are hydrocarbons, such as o-dichlorobenzene,tetralin, toluene and xylene, and furthermore ethers, such as dibutylether, glycol dimethyl ether and diglycol dimethyl ether, and also polarsolvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide andN-methyl-pyrrolidone.

[0458] All the customary acid acceptors can be used as acid acceptors incarrying out process (E) according to the invention.

[0459] Acid acceptors which can preferably be used are tertiary amines,such as triethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base orN,N-dimethyl-aniline.

[0460] The reaction temperature can be varied within a substantial rangein carrying out process (E) according to the invention. The reaction isexpediently carried out at temperatures between 0° C. and 250° C.,preferably between 20° C. and 220° C.

[0461] Process (E) according to the invention is expediently carried outunder normal pressure.

[0462] In carrying out process (E) according to the invention, thereaction components of the formulae (VII) and (VI) and if appropriatethe acid acceptors are in general employed in approximately equimolaramounts. However, it is also possible to use one or other of thecomponents in a larger excess (up to 5 mol).

[0463] Process (Fα) is characterized in that compounds of the formulae(I-1-a) to (I-5-a) are in each case reacted with carboxylic acid halidesof the formula (VIII), if appropriate in the presence of a diluent andif appropriate in the presence of an acid-binding agent.

[0464] Diluents which can be employed in process (Fα) according to theinvention are all the solvents which are inert towards the acid halides.Solvents which can preferably be used are hydrocarbons, such as benzine,benzene, toluene, xylene and tetralin, and furthermore halogenatedhydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, and also ketones,such as acetone and methyl isopropyl ketone, and furthermore ethers,such as diethyl ether, tetrahydrofuran and dioxane, and moreovercarboxylic acid esters, such as ethyl acetate, and also strongly polarsolvents, such as dimethylformamide, dimethyl sulphoxide and sulpholane.If the stability of the acid halide to hydrolysis allows, the reactioncan also be carried out in the presence of water.

[0465] Possible acid-binding agents in the reaction by process (Fα)according to the invention are all the customary acid acceptors. Acidacceptors which can preferably be used are tertiary amines, such astriethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base andN,N-dimethyl-aniline, and furthermore alkaline earth metal oxides, suchas magnesium oxide and calcium oxide, and also alkali metal and alkalineearth metal carbonates, such as sodium carbonate, potassium carbonateand calcium carbonate, as well as alkali metal hydroxides, such assodium hydroxide and potassium hydroxide.

[0466] The reaction temperature can be varied within a substantial rangein process (Fα) according to the invention. The reaction is in generalcarried out at temperatures between −20° C. and +150° C., preferablybetween 0° C. and 100° C.

[0467] In carrying out process (Fα) according to the invention, thestarting substances of the formulae (I-1-a) to (I-5-a) and thecarboxylic acid halide of the formula (VIII) are in general used inamounts which are in each case approaching equivalent amounts. However,it is also possible to employ the carboxylic acid halide in a largerexcess (up to 5 mol). Working up is carried out by customary methods.

[0468] Process (Fβ) is characterized in that compounds of the formulae(I-1-a) to (I-5-a) are in each case reacted with carboxylic acidanhydrides of the formula (IX), if appropriate in the presence of adiluent and if appropriate in the presence of an acid-binding agent.

[0469] Diluents which can be used in process (Fβ) according to theinvention are preferably those diluents which are also preferablypossible in the case where acid halides are used. A carboxylic acidanhydride employed in excess can moreover also simultaneously functionas the diluent.

[0470] Possible acid-binding agents which are added, if appropriate, inprocess (Fβ) are preferably those acid-binding agents which are alsopreferably possible when acid halides are used.

[0471] The reaction temperature can be varied within a substantial rangein process (Fβ) according to the invention. The reaction is in generalcarried out at temperatures between −20° C. and +150° C., preferablybetween 0° C. and 100° C.

[0472] In carrying out process (Fβ) according to the invention, thestarting substances of the formulae (I-1-a) to (I-5-a) and thecarboxylic acid anhydride of the formula (IX) are in general used inamounts which are in each case approaching equivalent amounts. However,it is also possible to employ the carboxylic acid anhydride in a largerexcess (up to 5 mol). Working up is carried out by customary methods.

[0473] In general, a procedure is followed in which the diluent and thecarboxylic acid anhydride present in excess as well as the carboxylicacid formed are removed by distillation or by washing with an organicsolvent or with water.

[0474] Process (G) is characterized in that compounds of the formulae(I-1-a) to (I-5-a) are in each case reacted with chloroformic acidesters or chloroformic acid thioesters of the formula (X), ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent.

[0475] Possible acid-binding agents in process (G) according to theinvention are all the customary acid acceptors. Acid acceptors which canpreferably be used are tertiary amines, such as triethylaamine,pyridine, DABCO, DBU, DBA, Hünig base and N,N-dimethyl-aniline, andfurthermore alkaline earth metal oxides, such as magnesium oxide andcalcium oxide, and also alkali metal and alkaline earth metalcarbonates, such as sodium carbonate, potassium carbonate and calciumcarbonate, as well as alkali metal hydroxides, such as sodium hydroxideand potassium hydroxide.

[0476] Diluents which can be employed in process (G) according to theinvention are all the solvents which are inert towards the chloroformicacid esters or chloroformic acid thioesters. Solvents which canpreferably be used are hydrocarbons, such as benzine, benzene, toluene,xylene and tetralin, and furthermore halogenated hydrocarbons, such asmethylene chloride, chloroform, carbon tetrachloride, chlorobenzene ando-dichlorobenzene, and also ketones, such as acetone and methylisopropyl ketone, and moreover ethers, such as diethyl ether,tetrahydrofuran and dioxane, and furthermore carboxylic acid esters,such as ethyl acetate, and also nitriles, such as acetonitrile, as wellas strongly polar solvents, such as dimethylformamide, dimethylsulphoxide and sulpholane.

[0477] The reaction temperature can be varied within a substantial rangein carrying out process (G) according to the invention. The reactiontemperature is in general between −20° C. and +100° C., preferablybetween 0° C. and 50° C.

[0478] Process (G) according to the invention is in general carried outunder normal pressure.

[0479] In carrying out process (G) according to the invention, thestarting substances of the formulae (I-1-a) to (I-5-a) and thecorresponding chloroformic acid esters or chloroformic acid thioestersof the formula (X) are in general used in amounts which are in each caseapproaching equivalent amounts. However, it is also possible to employone or other of the components in a larger excess (up to 2 mol). Workingup is carried out by customary methods. A procedure is in generalfollowed in which. salts which have precipitated out are removed and thereaction mixture which remains is concentrated by stripping off thediluent.

[0480] Process (H) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-5-a) are in each case reactedwith (Ha) compounds of the formula (XI) in the presence of a diluent andif appropriate in the presence of an acid-binding agent, or (HO) carbondisulphide and then with alkyl halides of the formula (XII), ifappropriate in the presence of a diluent and if appropriate in thepresence of a base.

[0481] In preparation process (Ha), about 1 mol of chloromonothioformicacid ester or chlorodithioformic acid ester of the formula (XI) isreacted per mol of starting compound of the formulae (I-1-a) to (I-5-a)at 0 to 120° C., preferably at 20 to 60° C.

[0482] Possible diluents which are added, if appropriate, are all theinert polar organic solvents, such as ethers, amides, sulphones,sulphoxides and also halogenoalkanes.

[0483] Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide ormethylene chloride are preferably employed.

[0484] If the enolate salt of the compounds (I-1-a) to (I-5-a) isprepared in a preferred embodiment by addition of strong deprotonatingagents, such as, for example, sodium hydride or potassium tert-butylate,further addition of acid-binding agents can be omitted.

[0485] If acid-binding agents are employed, then customary inorganic ororganic bases are possible, and examples which may be mentioned aresodium hydroxide, sodium carbonate, potassium carbonate, pyridine andtriethylamine.

[0486] The reaction can be carried out under normal pressure or underincreased pressure, and is preferably carried out under normal pressure.Working up is carried out by customary methods.

[0487] In preparation process (HO), in each case the equimolar amount oran excess of carbon disulphide is added per mol of starting compounds ofthe formulae (I-1-a) to (I-5-a). The reaction here is preferably carriedout at temperatures from 0 to 50° C., and in particular at 20 to 30° C.

[0488] It is often expedient first to prepare the corresponding saltfrom the compounds of the formulae (I-1-a) to (I-5-a) by addition of abase (such as, for example, potassium tert-butylate or sodium hydride).The compounds (I-1-a) to (I-5-a) are in each case reacted with carbondisulphide until the formation of the intermediate compound has ended,for example after stirring at room temperature for several hours.

[0489] All the customary proton acceptors can be employed as bases inprocess (HO). Proton acceptors which can preferably be used are alkalimetal hydrides, alkali metal alcoholates, alkali metal or alkaline earthmetal carbonates or bicarbonates or nitrogen bases. Examples which maybe mentioned are sodium hydride, sodium methanolate, sodium hydroxide,calcium hydroxide, potassium carbonate, sodium bicarbonate,triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline,diazabicyclooctane (DABCO), diazabicyclononene (DBN) anddiazabicycloundecene (DBU).

[0490] All the customary solvents can be used as diluents in thisprocess.

[0491] Solvents which can preferably be used are aromatic hydrocarbons,such as benzene or toluene, alcohols, such as methanol, ethanol,isopropanol or ethylene glycol, nitriles, such as acetonitrile, ethers,such as tetrahydrofuran or dioxane, amides, such as dimethylformamide,or other polar solvents, such as dimethyl sulphoxide or sulpholane.

[0492] Further reaction with the alkyl halide of the formula (XII) ispreferably carried out at 0 to 70° C., and in particular at 20 to 50° C.At least the equimolar amount of alkyl halide is employed in thisreaction.

[0493] The reaction is carried out under normal pressure or underincreased pressure, preferably under normal pressure.

[0494] Working up is again carried out by customary methods.

[0495] Process (I) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-5-a) are in each case reactedwith sulphonic acid chlorides of the formula (XIII), if appropriate inthe presence of a diluent and if appropriate in the presence of anacid-binding agent.

[0496] In preparation process (I), about 1 mol of sulphonic acidchloride of the formula (XIII) is reacted per mol of starting compoundof the formula (I-1-a to I-5-a) at −20 to 150° C., preferably at 0 to70° C.

[0497] Process (I) is preferably carried out in the presence of adiluent.

[0498] Possible diluents are all the inert polar organic solvents, suchas ethers, amides, ketones, carboxylic acid esters, nitriles, sulphones,sulphoxides or halogenated hydrocarbons, such as methylene chloride.

[0499] Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide andmethylene chloride are preferably employed.

[0500] If the enolate salt of the compounds (I-1-a) to (I-5-a) isprepared in a preferred embodiment by addition of strong deprotonatingagents (such as, for example, sodium hydride or potassiumtert-butylate), further addition of acid-binding agents can be omitted.

[0501] If acid-binding agents are employed, then customary inorganic ororganic bases are possible, and examples which may be mentioned aresodium hydroxide, sodium carbonate, potassium carbonate, pyridine andtriethylamine.

[0502] The reaction can be carried out under normal pressure or underincreased pressure, and is preferably carried out under normal pressure.Working up is carried out by customary methods.

[0503] Process (J) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-5-a) are in each case reactedwith phosphorus compounds of the formula (XIV), if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

[0504] In preparation process (J), 1 to 2, preferably 1 to 1.3, mol ofthe phosphorus compound of the formula (XIV) are reacted per mol of thecompounds (I-1-a) to (I-5-a) at temperatures between −40° C. and 150°C., preferably between −10 and 110° C., to give compounds of theformulae (I-1-e) to (I-6-e).

[0505] Process (J) is preferably carried out in the presence of adiluent.

[0506] Possible diluents are all the inert polar organic solvents, suchas ethers, carboxylic acid esters, halogenated hydrocarbons, ketones,amides, nitriles, sulphones, sulphoxides and the like.

[0507] Acetonitrile, dimethyl sulphoxide, tetrahydrofuran,dimethylformamide and methylene chloride are preferably employed.

[0508] Possible acid-binding agents, which are added if appropriate, arethe customary inorganic or organic bases, such as hydroxides, carbonatesor amines. Examples which may be mentioned are sodium hydroxide, sodiumcarbonate, potassium carbonate, pyridine and triethylamine.

[0509] The reaction can be carried out under normal pressure or underincreased pressure, and is preferably carried out under normal pressure.Working up is carried out by customary methods of organic chemistry. Theend products are preferably purified by crystallization, chromatographicpurification or by so-called “incipient distillation”, i.e. removal ofthe volatile constituents in vacuo.

[0510] Process (K) is characterized in that compounds of the formulae(I-1-a) to (I-5-a) are in each case reacted with metal hydroxides ormetal alkoxides of the formula (XV) or amines of the formula (XVI), ifappropriate in the presence of a diluent.

[0511] Diluents which can be employed in process (K) according to theinvention are preferably ethers, such as tetrahydrofuran, dioxane ordiethyl ether, or else alcohols, such as methanol, ethanol orisopropanol, or alternatively water. Process (K) according to theinvention is in general carried out under normal pressure. The reactiontemperature is in general between −20° C. and 100° C., preferablybetween 0° C. and 50° C.

[0512] Process (L) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-5-a) are in each case reactedwith (Lα) compounds of the formula (XVII), if appropriate in thepresence of a diluent and if appropriate in the presence of a catalyst,or with (Lβ) compounds of the formula (XVIII) if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

[0513] In preparation process (Lα), about 1 mol of isocyanate of theformula (XVII) is reacted per mol of starting compound of the formulae(I-1-a) to (I-5-a) at 0 to 100° C., preferably at 20 to 50° C.

[0514] Process (Lα) is preferably carried out in the presence of adiluent.

[0515] Possible diluents are all the inert organic solvents, such asaromatic hydrocarbons, halogenated hydrocarbons, ethers, amides,nitriles, sulphones or sulphoxides.

[0516] If appropriate, catalysts can be added to accelerate thereaction. Catalysts which can very advantageously be employed areorganotin compounds, such as, for example, dibutyltin dilaurate.

[0517] The reaction is preferably carried out under normal pressure.

[0518] In preparation process (Lβ), about 1 mol of carbamic acidchloride of the formula (XVIII) is reacted per mol of starting compoundof the formulae (I-1-a) to (I-5-a) at 0 to 150° C., preferably at 20 to70° C.

[0519] Possible diluents, which are added if appropriate, are all theinert polar organic solvents, such as ethers, carboxylic acid esters,nitriles, ketones, amides, sulphones, sulphoxides or halogenatedhydrocarbons.

[0520] Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide ormethylene chloride are preferably employed.

[0521] If the enolate salt of the compound (I-1-a) to (I-5-a) isprepared in a preferred embodiment by addition of strong deprotonatingagents (such as, for example, sodium hydride or potassiumtert-butylate), further addition of acid-binding agents can be omitted.

[0522] If acid-binding agents are employed, customary inorganic ororganic bases are possible, and examples which may be mentioned aresodium hydroxide, sodium carbonate, potassium carbonate, triethylamineor pyridine.

[0523] The reaction can be carried out under normal pressure or underincreased pressure, and is preferably carried out under normal pressure.Working up is carried out by customary methods.

[0524] The active compounds are suitable for controlling animal pests,preferably arthropods and nematodes, in particular insects andarachnids, which are encountered in agriculture, in forestry, in theprotection of stored products and of materials, and in the hygienefield. They are active against normally sensitive and resistant speciesand against all or some stages of development. The abovementioned pestsinclude:

[0525] From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

[0526] From the order of the Diplopoda, for example, Blaniulusguttulatus.

[0527] From the order of the Chilopoda, for example, Geophiluscarpophagus and Scutigera spec.

[0528] From the order of the Symphyla, for example, Scutigerellaimmaculata.

[0529] From the order of the Thysanura, for example, Lepisma saccharina.

[0530] From the order of the Collembola, for example, Onychiurusarmatus.

[0531] From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

[0532] From the order of the Dermaptera, for example, Forficulaauricularia.

[0533] From the order of the Isoptera, for example, Reticulitermes spp.

[0534] From the order of the Anoplura, for example, Phylloxeravastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp.and Linognathus spp.

[0535] From the order of the Mallophaga, for example, Trichodectes spp.and Damalinea spp.

[0536] From the order of the Thysanoptera, for example, Hercinothripsfemoralis and Thrips tabaci.

[0537] From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

[0538] From the order of the Homoptera, for example, Aleurodesbrassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii,Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi,Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzusspp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelisbilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae,Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii,Aspidiotus hederae, Pseudococcus spp. and Psylla spp.

[0539] From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

[0540] From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Hylotrupes bajulus,Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae,Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis,Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilusspp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchusassimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenusspp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor,Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallonsolstitialis and Costelytra zealandica.

[0541] From the order of the Hymenoptera, for example, Diprion spp.,Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp. Fromthe order of the Diptera, for example, Aedes spp., Anopheles spp., Culexspp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

[0542] From the order of the Siphonaptera, for example, Xenopsyllacheopis and Ceratophyllus spp.

[0543] From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

[0544] From the order of the Acarina, for example, Acarus siro, Argasspp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis,Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyommaspp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp.,Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. andTetranychus spp.

[0545] The active compounds according to the invention are distinguishedby a high insecticidal and acaricidal activity.

[0546] They can be employed particularly successfully against insectswhich are harmful to plants, such as, for example, against the larvae ofthe mustard beetle (Phaedon cochleariae) or against the larvae of therice green leafhopper (Nephotettix cincticeps) and against the larvae ofthe cabbage moth (Plutella maculipennis).

[0547] The active compounds according to the invention can furthermorebe used as defoliants, desiccants, agents for destroying broad-leavedplants and, especially, as weed-killers. By weeds, in the broadestsense, there are to be understood all plants which grow in locationswhere they are undesired. Whether the substances according to theinvention act as total or selective herbicides depends essentially onthe amount used.

[0548] The dosages of the active compounds according to the inventionnecessary for combating weeds are between 0.001 and 10 kg/ha, preferablybetween 0.005 and 5 kg/ha.

[0549] The active compounds according to the invention can be used, forexample, in connection with the following plants:

[0550] Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium,Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica,Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea,Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum,Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura,Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus andTaraxacum.

[0551] Dicotyledon cultures of the genera: Gossypium, Glycine, Beta,Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

[0552] Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cycnodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

[0553] Monocotyledon cultures of the genera: Oryza, Zea, Triticum,Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagusand Allium.

[0554] However, the use of the active compounds according to theinvention is in no way restricted to these genera, but also extends inthe same manner to other plants.

[0555] The compounds are suitable, depending on the concentration, forthe total combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hop fields, onornamental and sports lawns and meadow areas and for the selectivecombating of weeds in annual cultures.

[0556] The active compounds according to the invention are particularlysuitable for selectively combating monocotyledon weeds in dicotyledoncrops by the pre- and post-emergence method. For example, they can beemployed very successfully for combating harmful grasses in cotton orsugar beet.

[0557] The active compounds can be converted into the customaryformulations, such as solutions, emulsions, wettable powders,suspensions, powders, dusting agents, pastes, soluble powders, granules,suspension-emulsion concentrates, natural and synthetic materialsimpregnated with active compound, and very fine capsules in polymericsubstances.

[0558] These formulations are produced in a known manner, for example bymixing the active compounds with extenders, that is liquid solventsand/or solid carriers, optionally with the use of surface-active agents,that is emulsifying agents and/or dispersing agents and/or foam-formingagents.

[0559] In the case of the use of water as an extender, organic solventscan, for example, also be used as auxiliary solvents. As liquidsolvents, there are suitable in the main: aromatics, such as xylene,toluene or alkylnaphthalenes, chlorinated aromatics and chlorinatedaliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes ormethylene chloride, aliphatic hydrocarbons, such as cyclohexane orparaffins, for example petroleum fractions, mineral and vegetable oils,alcohols, such as butanol or glycol as well as their ethers and esters,ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

[0560] As solid carriers there are suitable:

[0561] for example, ammonium salts and ground natural minerals, such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals, such as highlydisperse silica, alumina and silicates; as solid carriers for granulesthere are suitable: for example, crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, as well assynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks; as emulsifying and/or foam-forming agents there are suitable:for example, non-ionic and anionic emulsifiers, such as polyoxyethylenefatty acid esters, polyoxyethylene fatty alcohol ethers, for examplealkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agentsthere are suitable: for example, lignin-sulphite waste liquors andmethylcellulose.

[0562] Adhesives such as carboxymethylcellulose and natural andsynthetic polymers in the form of powders, granules or latexes, such asgum arabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

[0563] It is possible to use colorants such as inorganic pigments, forexample iron oxide, titanium oxide and Prussian Blue, and organicdyestuffs, such as alizarin dyestuffs, azo dyestuffs and metalphthalocyanine dyestuffs, and trace nutrients such as salts of iron,manganese, boron, copper, cobalt, molybdenum and zinc.

[0564] The formulations in general contain between 0.1 and 95% by weightof active compound, preferably between 0.5 and 90%.

[0565] The active compound according to the invention can be present inits commercially available formulations and in the use forms preparedfrom these formulations as a mixture with other active compounds, suchas insecticides, baits, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphoric acid esters, carbamates, carboxylicacid esters, chlorinated hydrocarbons, phenylureas, substances producedby microorganisms, and the like.

[0566] Particularly favourable mixing partners are, for example, thefollowing:

[0567] Fungicides:

[0568] 2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxy-phenyl)acetamide;8-hydroxyquinoline sulphate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate; methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,

[0569] benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bvpirimate, buthiobate,

[0570] calcium polysulphide, captafol, captan, carbendazim, carboxin,quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate,cufraneb, cymoxanil, cyproconazole, cyprofuram,

[0571] dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,dinocap, diphenylamine, dipyrithion, ditalimfos, dithianon, dodine,drazoxolon,

[0572] edifenphos, epoxyconazole, ethirimol, etridiazole,

[0573] fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetyl-aluminum, fthalide, fuberidazole, furalaxyl, furmecyclox,

[0574] guazatine,

[0575] hexachlorobenzene, hexaconazole, hymexazol,

[0576] imazalil, imibenconazole, iminoctadine, iprobenfos (IBP),iprodione, isoprothiolane,

[0577] kasugamycin, copper preparations such as: copper hydroxide,copper naphthenate, copper oxychloride, copper sulphate, copper oxide,oxine-copper and Bordeaux mixture, mancopper, mancozeb, maneb,mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb,methfuroxam, metiram, metsulfovax, myclobutanil,

[0578] nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

[0579] ofurace, oxadixyl, oxamocarb, oxycarboxin,

[0580] pefurazoate, penconazole, pencycuron, phosdiphen, phthalide,pimaricin, piperalin, polycarbamate, polyoxin, probenazole, prochloraz,procymidone, propamocarb, propiconazole, propineb, pyrazophos,pyrifenox, pyrimethanil, pyroquilon, quintozene (PCNB),

[0581] sulphur and sulphur preparations,

[0582] tebuconazole, tecloftalam, tecnazene, tetraconazole,thiabendazole, thicyofen, thiophanate-methyl, thiram, tol clophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide,trichlamide, tricyclazole, tridemorph, triflumizole, triforine,triticonazole,

[0583] validamycin A, vinclozolin,

[0584] zineb, ziram

[0585] Bactericides:

[0586] bronopol, dichlorophen, nitrapyrin, nickeldimethyldithiocarbamate, kasugamycin, octhilinon, furancarboxylic acid,oxytetracyclin, probenazol, streptomycin, tecloftalam, copper sulphateand other copper preparations.

[0587] Insecticides/Acaricides/Nematicides:

[0588] abamectin, AC 303 630, acephate, acrinathrin, alanycarb,aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin,azinphos A, azinphos M, azocyclotin,

[0589]Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb,buprofezin, butocarboxin, butylpyri dab en,

[0590] cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,cartap, CGA 157 419, CGA 184 699, chloethocarb, chlorethoxyfos,chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifosM, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,

[0591] deltamethrin, demeton-M, demeton-S, demeton-S-methyl,diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos,dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos,dioxathion, disulfoton,

[0592] edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion,ethofenprox, ethoprophos, etrimphos,

[0593] fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad,fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate,fonophos, formothion, fosthiazate, fubfenprox, furathiocarb,

[0594] HCH, heptenophos, hexaflumuron, hexythiazox,

[0595] imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb,isoxathion, ivermectin,

[0596] lambda-cyhalothrin, lufenuron,

[0597] malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde,methacrifos, methamidophos, methidathion, methiocarb, methomyl,metolcarb, milbemectin, monocrotophos, moxidectin,

[0598] naled, NC 184, NI 25, nitenpyram,

[0599] omethoate, oxamyl, oxydemethon M, oxydeprofos,

[0600] parathion A, parathion M, permethrin, phenthoate, phorate,phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos,prothoate, pymetrozin, pyrachlophos, pyraclofos, pyrachlophos,pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen,pyriproxifen,

[0601] quinalphos,

[0602] RH 5992,

[0603] salithion, sebufos, silafluofen, sulfotep, sulprofos,

[0604] tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron,tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox,thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin,tralomethrin, triarathen, triazophos, triazuron, trichlorfon,triflumuron, trimethacarb,

[0605] vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

[0606] Herbicides:

[0607] for example anilides, such as, for example, diflufenican andpropanil; arylcarboxylic acids such as, for example, dichloropicolinicacid, dicamba and picloram; aryloxyalkanoic acids, such as, for example,2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr;aryloxy-phenoxy-alkanoic acid esters, such as, for example,diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl andquizalofop-ethyl; azinones, such as, for example, chloridazon andnorflurazon; carbamates, such as, for example, chlorpropham,desmedipham, phenmedipham and propham; chloroacetanilides, such as, forexample, alachlor, acetochlor, butachlor, metazachlor, metolachlor,pretilachlor and propachlor; dinitroanilines, such as, for example,oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as, forexample, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen,lactofen and oxyfluorfen; ureas, such as, for example, chlortoluron,diuron, fluometuron, isoproturon, linuron and methabenzthiazuron;hydroxylamines, such as, for example, alloxydim, clethodim, cycloxydim,sethoxydim and tralkoxydim; imidazolinones, such as, for example,imazethapyr, imazamethabenz, imazapyr and imazaquin; nitriles, such as,for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides, suchas, for example, mefenacet; sulfonylureas, such as, for example,amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron,cinosulfuron, metsulfuronmethyl, nicosulfuron, primisulfuron,pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron andtribenuron-methyl; thiocarbamates, such as, for example, butylate,cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb,thiobencarb and triallate; triazines, such as, for example, atrazine,cyanazine, simazine, simetryn, terbutryn and terbutylazine; triazinones,such as, for example, hexazinone, metamitron and metribuzin; others,such as, for example, aminotriazole, benfuresate, bentazone,cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr,ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben,pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

[0608] The active compound according to the invention can furthermore bepresent in its commercially available formulations and in the use forms,prepared from these formulations, as a mixture with synergistic agents.Synergistic agents are compounds which increase the action of the activecompounds without it being necessary for the synergistic agent added tobe active itself

[0609] The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

[0610] The compounds are used in a customary manner appropriate for theuse form.

[0611] When used against hygiene pests and pests of stored products, theactive compound is distinguished by an outstanding residual action onwood and clay and by a stability to alkali on limed substrates.

[0612] The active compounds according to the invention have an actionnot only against plant and hygiene pests and pests of stored products,but also in the veterinary medicine sector against animal parasites(ectoparasites), such as hard ticks, soft ticks, mange mites, harvestmites, flies (biting and licking), parasitic fly. larvae, lice, hairlice and fleas. These parasites include:

[0613] From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

[0614] From the order of the Mallophagida and the suborders Amblycerinaand Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinotonspp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

[0615] From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp, Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

[0616] From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

[0617] From the order of the Heteropterida, for example, Cimex spp.,Triatoma spp., Rhodnius spp. and Panstrongylus spp.

[0618] From the order of the Blattrida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

[0619] From the sub-class of the Acaria (Acarida) and the orders of theMeta- and Mesostigmata, for example, Argas spp., Omithodorus spp.,Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentorspp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssusspp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroaspp.

[0620] From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trmbicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

[0621] For example, they show an outstanding activity against Boophilusmicroplus and Lucilia cuprina.

[0622] The active compounds of the formula (I) according to theinvention are also suitable for combating arthropods which infestagricultural productive livestock such as, for example, cattle, sheep,goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens,turkeys, ducks, geese and bees, other pets, such as, for example, dogs,cats, cage birds and aquarium fish, and also so-called test animals,such as, for example, hamsters, guinea pigs, rats and mice. By combatingthese arthropods cases of death and reductions in productivity (formeat, milk, wool, hides, eggs, honey etc) should be diminished, so thatmore economic animal husbandry is possible by use of the activecompounds according to the invention.

[0623] The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boli, the feed-through process and suppositories, by parenteraladministration, such as, for example, by injections (intra-muscular,subcutaneous, intravenous, intraperitoneal etc), implants, by nasaladministration, by dermal use in the form, for example, of dipping orbathing, spraying, pouring on and spotting on, washing and powdering,and also with the aid of moulded articles containing the activecompound, such as collars, ear marks, tail marks, limb bands, halters,marking devices, etc.

[0624] When used for livestock, poultry, pets and the like, the activecompounds of the formula (I) can be used as formulations (for examplepowders, emulsions, compositions capable of flow) which comprise theactive compounds in an amount of 1 to 80% by weight, directly or after100 to 10,000-fold dilution, or they can be used as a chemical bath.

[0625] It has furthermore been found that the compounds of the formula Iaccording to the invention display a high insecticidal action againstinsects which destroy industrial materials.

[0626] The following insects may be mentioned as examples and preferredbut without being limited:

[0627] Beetles, such as

[0628]Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex,Emobius mollis, Priobium carpini, Lyctus Brunneus, Lyctus africanus,Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylonaequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec, Apatemonachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylonspec. and Dinoderus minutus.

[0629] Hymenopterans, such as

[0630]Sirex Juvencus, Urocerus gigas, Urocerus gigas taignus andUrocerus augur.

[0631] Termites, such as

[0632]Kalotermes flavicollis, Cryptotermes brevis, Heterotermesindicola, Reticulitermes flavipes, Reticulitermes santonensis,Reticuitermes lucifugus, Mastotermes darwiniensis, Zootermopsisnevadensis and Coptotermes formosanus.

[0633] Bristle-Tails

[0634] such as Lepisma saccharina.

[0635] Industrial materials in the present connection are to beunderstood as meaning non-living materials, such as, preferably,plastics, adhesives, sizes, papers and cards, leather, wood andprocessed wood products, and lacquers and paints.

[0636] Material to be preserved from insect damage which is quiteparticularly preferred is wood and processed wood products.

[0637] Wood and processed wood products which can be protected by theagents according to the invention or mixtures comprising these are to beunderstood as meaning, for example: building timber, wooden beams,railway sleepers, bridge components, boat gangplanks, wooden vehicles,crates, pallets, containers, telegraph masts, wood lagging, woodenwindows and doors, plywood, chipboards, joinery or wood products usedquite generally in house construction or building joinery.

[0638] The active compounds can be used as such or in the form ofconcentrates or generally customary formulations, such as powders,granules, solutions, suspensions, emulsions or pastes.

[0639] The formulations mentioned can be prepared in a manner known perse, for example by mixing the active compounds with at least one solventor diluent, emulsifier, dispersing agent and/or binder or fixing agent,water repellant, optionally siccatives and UV stabilizers, and ifappropriate dyestuffs and pigments, as well as other processingauxiliaries.

[0640] The insecticidal compositions or concentrates used forpreservation of wood and derived timber products comprise the activecompound according to the invention in a concentration of 0.0001 to 95%by weight, in particular 0.001 to 60% by weight.

[0641] The amount of composition or concentrate employed depends on thenature and the occurrence of the insects and on the medium. The optimumamount employed for the use can in each case be determined by a seriesof tests. In general, however, it is sufficient to employ 0.0001 to 20%by weight, preferably 0.001 to 10% by weight, of the active compoundbased on the material to be preserved.

[0642] The solvent and/or diluent used is an organochemical solvent orsolvent mixture and/or an oily or oil-like organochemical solvent orsolvent mixture of low volatility and/or a polar organochemical solventor solvent mixture and/or water and, if appropriate, an emulsifierand/or wetting agent.

[0643] Oily or oil-like solvents having an evaporation number above 35and a flash point above 30° C., preferably above 45° C., are preferablyemployed as organochemical solvents. Corresponding mineral oils oraromatic fractions thereof or solvent mixtures containing mineral oil,preferably white spirit, petroleum and/or alkylbenzene, are used as suchwater-insoluble, oily and oil-like solvents of low volatility.

[0644] Mineral oils having a boiling range from 170 to 220° C., whitespirit having a boiling range from 170 to 220° C., spindle oil having aboiling range from 250 to 350° C., petroleum or aromatics having aboiling range from 160 to 280° C., terpentine oil and the like areadvantageously employed.

[0645] In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are employed.

[0646] The organic oily or oil-like solvents of low volatility having anevaporation number above 35 and a flash point above 30° C., preferablyabove 45° C., can be replaced in part by organochemical solvents of highor medium volatility, provided that the solvent mixture likewise has anevaporation number above 35 and a flash point above 30° C., preferablyabove 45° C., and that the insecticide/fungicide mixture is soluble orcan be emulsified in this solvent mixture.

[0647] According to a preferred embodiment, some of the organochemicalsolvent or solvent mixture is replaced by an aliphatic polarorganochemical solvent or solvent mixture. Aliphatic organochemicalsolvents containing hydroxyl and/or ester and/or ether groups, such as,for example, glycol ethers, esters or the like, are preferably used.

[0648] Organochemical binders which are the synthetic resins and/orbinding drying oils which are water-dilutable and/or soluble ordispersible or emulsifiable in the organochemical solvents employed andare known per se, in particular binders consisting of or comprising anacrylate resin, a vinyl resin, for example polyvinyl acetate, polyesterresin, polycondensation or polyaddition resin, polyurethane resin, alkydresin or modified alkyd resin, phenolic resin, hydrocarbon resin, suchas indene-coumarone resin or silicone resin, drying plant and/or dryingoils and/or binders which dry by physical means and are based on anaturally occurring and/or synthetic resin.

[0649] The synthetic resin used as the binder can be employed in theform of an emulsion, dispersion or solution. Bitumen or bituminoussubstances can also be used as binders in an amount of up to 10% byweight. In addition, dyestuffs, pigments, water-repellant agents, odourcorrectants and inhibitors or corrosion prevention agents and the likewhich are known per se can be employed.

[0650] Preferably, according to the invention, the composition orconcentrate comprises at least one alkyd resin or modified alkyd resinand/or one drying plant oil as an organochemical binder. Alkyd resinshaving an oil content of more than 45% by weight, preferably 50 to 68%by weight, are preferably used according to the invention.

[0651] All or some of the binder mentioned can be replaced by a fixingagent (mixture) or a plasticizer (mixture). These additives are intendedto prevent evaporation of the active compounds and crystallization orprecipitation They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

[0652] The plasticizers originate from the chemical classes of phthalicacid esters, such as dibutyl, dioctyl or benzyl butyl phthalate,phosphoric acid esters, such as tributyl phosphate, adipic acid esters,such as di-(2-ethylhexyl) adipate, stearates, such as butyl stearate oramyl stearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

[0653] Fixing agents are based chemically on polyvinyl alkyl ethers,such as, for example, polyvinyl methyl ether, or ketones, such asbenzophenone or ethylenebenzophenone.

[0654] Water in particular is also a possible solvent or diluent, ifappropriate mixed with one or more of the abovementioned organochemicalsolvents or diluents, emulsifiers and dispersing agents.

[0655] Particularly effective wood preservation is achieved byimpregnation processes on a large industrial scale, for example vacuum,a double vacuum or pressure processes.

[0656] If appropriate, the ready-to-use compositions can also compriseother insecticides, and if appropriate also one or more fungicides.

[0657] Possible additional admixing partners are, preferably, theinsecticides and fungicides mentioned in WO 94/29 268. The compoundsmentioned in this document are an express constituent of the presentapplication.

[0658] Especially preferred admixing partners can be insecticides, suchas chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin,cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron, and fungicides, such asepoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid,3-iodo-2-propinyl butylcarbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octyli sothiazolin-3-one.

[0659] The preparation and the use of the active compounds according tothe invention can be seen from the following examples.

PREPARATION EXAMPLES Example (I-1-a-1)

[0660]

[0661] 25.0 g (0.072 mol) of the compound according to Example (II-2) in150 ml of anhydrous toluene are added dropwise to 18.5 g (0.165 mol) ofpotassium tert-butylate in 57 ml of anhydrous tetrahydrofuran (THF) atthe reflux temperature and the mixture is stirred under reflux for 1.5hours. For working up, 220 ml of water are added, the aqueous phase isseparated off, the toluene phase is extracted with 110 ml of water andthe aqueous phases are combined, washed with toluene and acidified withabout 26 ml of concentrated HCl at 10 to 20° C. The product is filteredoff with suction, washed, dried and washed by stirring in methyltert-butyl (MTB) ether/n-hexane.

[0662] Yield: 18.0 g (79% of theory), melting point: 159° C.

[0663] The following compounds of the formula (I-1-a) are obtainedanalogously and in accordance with the general information on thepreparation: TABLE I (I-l-a)

Melting Example point Iso- No. X Y Z A B °C. mer I-1-a-2 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— >220 β I-1-a-3 Cl Cl Cl—(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-4 CH₃ Cl CH₃—(CH₂)₂—CHCH₃—(CH₂)₂ >220 β I-1-a-5 CH₃ CH₃ CH₃ —(CH₂)₂—O—(CH₂)₂— >220I-1-a-6 CH₃ Br Cl —(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-7 Br CH₃ Cl—(CH₂)₂—CHCH₃—(CH₂)₂— 221 β I-1-a-8 Cl —O—CF₂—O— —(CH₂)₂—CHCH₃—(CH₂)₂—180 β dec. I-1-a-9 Br —(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-10 ClCH₃ Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— 208 β I-1-a-11 Br CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-12 CH₃ Br CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂—208 β I-1-a-13 Cl Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— 206 β I-1-a-14 Cl Br CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-15 Br CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— >220 β

Example (I-1-b-1)

[0664]

[0665] 1.13 ml (0.015 mol) of acetyl chloride in 5 ml of absolutemethylene chloride are added to 4.5 g (0.015 mol) of the compoundaccording to Example (I-1-a-1) and 2.1 ml (15 mmol) of triethylamine in70 ml of absolute methylene chloride at 0 to 10° C. The mixture isstirred at room temperature until, according to monitoring by thin layerchromatography, the reaction has ended. For working up, the mixture iswashed twice with 50 ml of 0.5 N sodium hydroxide solution, dried overmagnesium sulphate and evaporated. The crude product is recrystallizedfrom MTB ether/n-hexane.

[0666] Yield: 3.4 g (66% of theory), melting point: 209° C.

[0667] The following compounds of the formula (I-b-1) are obtainedanalogously and in accordance with the general information on thepreparation: TABLE 2 (I-1-b)

Melting Example point Iso- No. X Y Z A B R¹ ° C. mer I-1-b-2 CH₃ CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 208 β I-1-b-3 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇ 152 β I-1-b-4 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇ 194 α* I-1-b-5 Cl Cl Cl—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ >220 β I-1-b-6 CH₃ CH₃ CH₃—(CH₂)₂—O-(CH₂)₂— i-C₃H₇ >220 — I-1-b-7 CH₃ Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂—i-C₃H₇ 213 β I-1-b-8 CH₃ Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— i-C₄H₉ 208 βI-1-b-9 Cl Br CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 187 β I-1-b-10 Br CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 151 β 1-1-b-11 Br CH₃ Cl—(CH₂)₂—CHCH₃—(CH₂)₂— t-C₄H₉ 217 β I-1-b-12 Br CH₃ Cl—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 198 β I-1-b-13 CH₃ Br Cl—(CH₂)₂—CHCH₃—(CH₂)₂— t-C₄H₉ 194 β I-1-b-14 CH₃ Br CI—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ >220 β

[0668]

[0669] 1.5 ml (15 mmol) of ethyl chloroformate in 5 ml of absolutemethylene chloride are added dropwise to 4.5 g (0.015 mol) of thecompound according to Example (I-1-a-1) and 2.1 ml of triethylamine in70 ml of absolute methylene chloride at 0 to 10° C. and the mixture isstirred at room temperature until, according to monitoring by thin layerchromatography, the reaction has ended. For working up, the mixture iswashed twice with 50 ml of 0.5 N sodium hydroxide solution, dried overmagnesium sulphate and evaporated.

[0670] Yield: 3.3 g (59% of theory), melting point: 193° C.

[0671] The following compounds of the formula (I-1-c) are obtainedanalogously and in accordance with the general information on thepreparation: TABLE 3 (I-1-c)

Melting Example point Iso- No. X Y Z A B L M R² ° C. mer I-1-c-2 CH₃ CH₃CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— O O i-C₄H₉ 119 β I-1-c-3 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— O O i-C₄H₉ 207 α* I-1-c-4 CH₃ Br Cl—(CH₂)₂—CHCH₃—(CH₂)₂— O O C₂H₅ >220 β I-1-c-5 CH₃ CH₃ CH₃—(CH₂)₂—O—(CH₂)₂— O O i-C₄H₉ 205 — I-1-c-6 Cl Cl Cl—(CH₂)₂—CHCH₃—(CH₂)₂— O O i-C₄H₉ 215 β I-1-c-7 CH₃ Cl CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— O O C₂H₅ 210 β I-1-c-8 CH₃ Cl CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— O O i-C₄H₉ 214 β I-I-c-9 Cl Br CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— O O C₂H₅ 223 β

Example II-1

[0672]

[0673] 17.5 g of the compound according to Example (XMX-1) in about 100ml of methylene chloride are cautiously added dropwise to 30.3 g (0.308mol) of concentrated sulphuric acid at 30 to 40° C. and the mixture isstirred at this a temperature for 2 hours. 41 ml of absolute methanolare then added dropwise such that an internal temperature of about 40°C. is established, and the mixture is stirred at 40 to 70° C. for afurther 6 hours.

[0674] For working up, the mixture is poured onto 0.29 kg of ice,extracted with methylene chloride, washed with aqueous sodiumbicarbonate solution, dried and evaporated. The crude product ispurified by column chromatography over silica gel using the mobile phasemethylene chloride/ethyl acetate 2:1.

[0675] Yield: 13.1 g (67% of theory), melting point: 147° C.

Example (II-2)

[0676]

[0677] 40.9 g (0.23 mol) of 2,4,5-trimethylphenylacetic acid and 33.6 ml(0.461 mol) of thionyl chloride are stirred at room temperature for 30minutes and then at 50° C. until the evolution of gas has ended. Excessthionyl chloride is removed at 50° C. in vacuo. 50 ml of absolutetoluene are then added and the mixture is evaporated again. The residueis taken up in 100 ml of absolute THF (solution 1).

[0678] Solution 1 is added to 47.9 g of methylcis-4-methylcyclohexylamine-1-carboxylate and 64.6 ml (0.460 mol) oftriethylamine in 600 ml of absolute THF at 0 to 10° C. and the mixtureis then stirred at room temperature for 1 hour. It is then filtered withsuction, washed with absolute THF and evaporated. The residue is takenup in methylene chloride and the mixture is washed with 0.5 N HCl, driedand evaporated. The crude product is purified by column chromatographyover silica gel using methylene chloride/ethyl acetate 7:1.

[0679] Yield: 25 g (32% of theory), melting point: 158° C.

[0680] The following compounds of the formula (II) are preparedanalogously to Examples (II-1) and (II-2) and in accordance with thegeneral information on the preparation. TABLE 4 (II)

Melting Example point Iso- No. X Y Z A B R⁸ ° C. mer II-3 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃— CH₃ 161 β (CH₂)₂— II-4 CH₃ Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂—CH₃ 192 β II-5 Cl Cl Cl —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 194 β II-6 Cl Br CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 196 β II-7 Cl CN CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃163 β II-8 Br Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 170 β II-9 Br CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 158 β II-10 CH₃ Br Cl —(CH₂)₂—CHCH₃—(CH₂)₂—CH₃ 197 β II-11 F Cl OCH₃ i-C₃H₇ CH₃ CH₃ 109- — 111 II-12 Cl —O—CF₂—O——(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 164 β II-13 Cl Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂—CH₃ 189 β II-14 CH₃ Br CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 171 β II-15 CH₃ ClCH₃ —(CH₂)₂—CHOCH₃— CH₃ 173 β (CH₂)₂— II-16 CH₃ Br CH₃ —(CH₂)₂—CHOCH₃—CH₃ 183 β (CH₂)₂— II-17 Br CH₃ CH₃ —(CH₂)₂—CHOCH₃— CH₃ 142 β (CH₂)₂—II-18 Cl Br CH₃ —(CH₂)₂—CHOCH₃— CH₃ β (CH₂)₂— II-19 CH₃ CH₃ CH₃ CH₃ CH₃CH₃ 159 — II-20 CH₃ CH₃ CH₃ i-C₃H₇ CH₃ CH₃ II-21 Cl CH₃ Cl—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 150 β II-22 Br CH₃ Cl —(CH₂)₂—CHOCH₃— CH₃ β(CH₂)₂— II-23 Cl Cl F —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 171 β II-24 Cl Cl F—(CH₂)₂—CHOCH₃— CH₃ 182 β (CH₂)₂— II-25 Br —(CH₂)₃——(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 168 β

Example (XXIX-1)

[0681]

[0682] Starting from 17.8 g of 2,4,5-trimethylphenylacetic acid,solution 1 is prepared as in Example (II-2).

[0683] Solution 1 is added dropwise to 16.8 g of1-amino-tetrahydropyran-1-carboxylic acid nitrile (70% pure) and 16.8 ml(0.12 mol) of triethylamine in 150 ml of absolute THF at 0 to 10° C. andthe mixture is stirred at room temperature for a further hour. It isthen evaporated, the residue is taken up in methylene chloride and themixture is washed with 0.5 N HCl, dried and evaporated. The crudeproduct is recrystallized from MTB ether/n-hexane.

[0684] Yield: 17.5 g (61% of theory), melting point: 156° C.

Example (I-2-a-1)

[0685]

[0686] 8.42 g (75 mmol) of potassium tert-butylate are initiallyintroduced into 50 ml of dimethylformamide, a solution of 16.6 g (50mmol) of 1-ethyloxycarbonylcyclohexyl 2,4,5-trimethyl-phenylacetateaccording to Example (III-1) in 50 ml of dimethylformamide is addeddropwise at 0 to 10° C. and the mixture is stirred overnight at roomtemperature.

[0687] For working up, the reaction mixture is added dropwise in 500 mlof ice-cold 1 N HCl and the product which has precipitated out isfiltered off with suction, washed with water and dried in a vacuumdrying cabinet. For further purification, the crude product is boiled upfurther with n-hexane/acetone.

[0688] Yield: 9.2 g (64% of theory) of melting point: 209-212° C.

[0689] The following compounds of the formula (I-2-a) are obtainedanalogously and in accordance with the general information on thepreparation: TABLE 5 (I-2-a)

Melting Example point No. X Y Z A B ° C. I-2-a-2 CH₃ CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— 190- 193 I-2-a-3 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— 167- 170 1-2-a-4 CH₃ Cl CH₃ —(CH₂)₅— 241- 2431-2-a-5 Cl Cl Cl —(CH₂)₅— 288 I-2-a-6 CH₃ Br Cl —(CH₂)₅— 242- 243I-2-a-7 CH₃ Br Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— 153- 154 I-2-a-8 Cl Br CH₃—(CH₂)₅— 232- 233 I-2-a-9 Cl Br CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— 167- 177I-2-a-10 F Cl OCH₃ CH₃ CH₃ 118- 120 I-2-a-11 Cl —O—CF₂—O— —(CH₂)₅— 247I-2-a-12 Cl CN CH₃ —(CH₂)₅— 220- 225

Example (I-2-b-1)

[0690]

[0691] 2.86 g (10 mmol) of the compound according to Example I-2-a-1 areinitially introduced into 40 ml of methylene chloride, 1.52 g (15 mmol)of triethylamine are added, a solution of 1.57 g (13 mmol) of pivaloylchloride in 40 ml of methylene chloride is added dropwise, while coolingwith ice, and the mixture is subsequently stirred at room temperaturefor 1 to 2 hours. For working up, the mixture is washed successivelywith 10% strength citric acid, 1N NaOH and NaCl solution and the organicphase is dried over MgSO₄ and evaporated. For further purification, thecrude product is stirred further with a little petroleum ether.

[0692] Yield: 3.0 g (81% of theory) of melting point: 128-132° C.

[0693] The following compounds of the formula (I-2-b) are obtainedanalogously and in accordance with the general information on thepreparation: TABLE 6 (I-2-b)

Melting Example point No. X Y Z A B R¹ ° C. I-2-b-2 CH₃ CH₃ CH₃ —(CH₂)₅—i-C₃H₇— 85-88 I-2-b-3 CH₃ CH₃ CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— t-C₄H₉— 139-143I-2-b-4 CH₃ CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇— 114-118 I-2-b-5 CH₃CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉— 125-129 I-2-b-6 Cl Cl Cl —(CH₂)₅—t-C₄H₉— 149 I-2-b-7 Cl Cl Cl —(CH₂)₅— t-C₄H₉—CH₂— 133 I-2-b-8 CH₃ Br Cl—(CH₂)₅— t-C₄H₉—CH₂— 146-147 I-2-b-9 CH₃ Br Cl —(CH₂)₅— t-C₄H₉— 168I-2-b-10 CH₃ Br Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇— 132-133 I-2-b-11 CH₃Br Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉— 145-149 I-2-b-12 CH₃ Cl CH₃—(CH₂)₅— t-C₄H₉— 160 I-2-b-13 CH₃ Cl CH₃ —(CH₂)₅— t-C₄H₉—CH₂— 157I-2-b-14 Cl Br CH₃ —(CH₂)₅— t-C₄H₉—CH₂— 161-162 I-2-b-15 Cl Br CH₃—(CH₂)₅— t-C₄H₉— 170 I-2-b-16 Cl Br CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇—98-99 I-2-b-17 Cl Br CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉— 139-140 I-2-b-18Cl —O—CF₂—O— —(CH₂)₅— t-C₄H₉— 125

Example (III-1)

[0694]

[0695] 8.9 g (50 mmol) of 2,4,5-trimethyl-phenylacetic acid areinitially introduced into 50 ml of toluene, 11.9 g (100 mmol) of thionylchloride are added and the mixture is stirred at 80° C. until theevolution of hydrogen chloride has ended and is then evaporated. Thecrude acid chloride is boiled in 50 ml of toluene together with 8.6 g(50 mmol) of ethyl 1-hydroxy-cyclohexanecarboxylate overnight and themixture is then evaporated.

[0696] Yield: 18.6 g (quantitative) of 1-ethoxycarbonyl-cyclohexyl2,4,6-trimethylphenylacetate as a colourless oil.

[0697] The following compounds of the formula (III) are obtainedanalogously and in accordance with the general instructions forpreparation: TABLE 7 (III)

Melting Example point No. X Y Z A B R⁸ ° C. III-2 CH₃ CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— C₂H₅ oil III-3 CH₃ CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂—C₂H₅ oil III-4 CH₃ Cl CH₃ —(CH₂)₅— C₂H₅ oil III-5 Cl Cl Cl —(CH₂)₅— C₂H₅oil III-6 CH₃ Br Cl —(CH₂)₅— C₂H₅ oil III-7 CH₃ Br Cl—(CH₂)₂—CHOCH₃—(CH₂)₂— C₂H₅ oil III-8 Cl Br CH₃ —(CH₂)₅— C₂H₅ oil III-9Cl Br CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— C₂H₅ oil III-10 F Cl OCH₃ CH₃ CH₃ C₂H₅oil III-11 Cl —O—CF₂—O— —(CH₂)₅— C₂H₅ oil III-12 Cl CN CH₃ —(CH₂)₅— C₂H₅oil

Example (I-3-a-1)

[0698]

[0699] 26.0 g (60.7 mmol) of the compound according to Example (IV-1)are heated under reflux with 55 ml of trifluoroacetic acid in 110 ml oftoluene for 3 hours. Excess trifluoroacetic acid is removed in vacuo,400 ml of water and 120 ml of MTB ether are added to the residue and thepH is brought to 14 with NaOH. The mixture is extracted twice with MTBether and the aqueous phase is acidified with concentrated HCl andextracted 3 times with MTB ether. The organic phases are dried andconcentrated. Yield 8.8 g (52% of theory), melting point 160 to 162° C.

Example (I-3-b-1)

[0700]

[0701] Preparation:

[0702] 1.0 g (3.6 mmol) of the compound according to Example I-3-a-1 areinitially introduced into 15 ml of absolute methylene chloride, and 0.75ml of triethylamine is added. A solution of 0.82 g (4.68 mmol) of6-chloronicotinyl chloride in 3 ml of absolute methylene chloride isadded dropwise, while cooling with ice. The mixture is stirred at roomtemperature for 2 hours. It is washed twice with 10% strength citricacid and the combined aqueous phases are extracted with methylenechloride. The combined organic phases are washed twice with 1 N NaOH andthe aqueous alkaline phases are extracted with methylene chloride.Finally, the combined organic phases are dried and concentrated and theresidue is stirred with petroleum ether. Yield 1.37 g (91% of theory),melting point 123 to 126° C.

[0703] The compounds of the formula I-3-b listed in the following tablewere prepared analogously to Example I-3-b-1 and in accordance with thegeneral description. I-3-b

Example No. X Y Z A B R¹ Melting point ° C. I-3-b-2 CH₃ CH₃ CH₃ C₂H₅ CH₃t-C₄H₉ oil I-3-b-3 CH₃ CH₃ CH₃ C₂H₅ CH₃ Cyclopropyl oil I-3-b-4 CH₃ CH₃CH₃ C₂H₅ CH₃ Cl—CH₂—C(CH₃)₂ oil

Example (I-3-c-1)

[0704]

[0705] Preparation:

[0706] 1.0 g (3.6 mmol) of the compound according to Example I-3-a-1 areinitially introduced into 15 ml of absolute methylene chloride, and 0.75ml (1.5 equivalents) of triethylamine is added. A solution of 0.61 ml(0.64 g; 4.68 mmol) of isobutyl 6-chloroformate in 3 ml of absolutemethylene chloride is added dropwise, while cooling with ice. Themixture is stirred at room temperature for 2 hours. It is washed twicewith 10% strength citric acid and the combined aqueous phases areextracted with methylene chloride. The combined organic phases arewashed twice with 1 N NaOH and the aqueous alkaline phases are extractedwith methylene chloride. Finally, the combined organic phases are driedand concentrated.

[0707] Yield 1.32 g (97% of theory), oil

[0708]¹H-NMR (400 MHz, DMSO):

[0709] δ=0.60-0.70 m, 6H, CH(CH₃)₂

[0710] 1.00-1.05 m, 3H, CH₂CH₃

[0711] 1.50-1.60 m, 1H, CH(CH₃)₂

[0712] 1.70-1.76 d, 3H, C(CH₃)

[0713] 1.90-2.02 m, 2H, CH₂CH₃

[0714] 2.05-2.20 m, 9H, ArCH₃

[0715] 3.65-3.72 m, 2H, OCH₂

[0716] 6.75-6.80 d, 1H, ortho Ar—H

[0717] 7.01 s, 1H, meta Ar—H

Example (I-3-c-2)

[0718] The compound of the formula (I-3-c-2) was obtained analogously toExample (I-3-c-1) as an oil:

Example (IV-1)

[0719]

[0720] A: 25 g (98 mmol) of the compound of the formula (XXXII-1)

[0721] 1 drop of dimethylformamide are stirred with 17.5 g (147 mmol) ofthionyl chloride in 100 ml of toluene at room temperature for 5 minutesand then at 100° C. until the evolution of gas has ended. Volatileconstituents are removed under a high vacuum.

[0722] B: 72 ml (118 mmol) of butyllithium (1.6 M) are added dropwise to18 ml (130 mmol) of diisopropylamine in 100 ml of THF, while coolingwith ice, and the mixture is stirred at this temperature for a further15 minutes. 18.8 g (108 mmol) of the compound according to Example(XXIV-3), dissolved in 40 ml of THF, are then added dropwise at 0° C.and the mixture is stirred at this temperature for 30 minutes. The acidchloride prepared according to A, dissolved in 40 ml of THF, is thenadded dropwise at 0° C. and the mixture is stirred at room temperaturefor 1 hour. 350 ml of MTB ether and a few drops of water are then addedand the mixture is extracted twice with 10% strength ammonium chloridesolution, dried and concentrated. The crude product (40 g) is purifiedby column chromatography (mobile phase cyclohexane/ethyl acetate 10/1).Yield 27.0 g (64% of theory), oil.

[0723]¹H-NMR (CDCl₃, 400 MHz):

[0724] δ=0.80-0.95 m, 3H, CH₂CH₃

[0725] 1.42 s, 3H, C—CH₃

[0726] 1.65-2.05 m, 2H, CH₂CH₃

[0727] 2.15-2.35 m, 9H, ArCH₃

[0728] 3.10-3.45 m, 2H, SCH₂

[0729] 3.70-3.80 m, 6H, OCH₃

[0730] 6.70-7.30 m, 6H, Ar—H

Example (I-4-a-1)

[0731]

[0732] 6.7 g (30 mmol) of 2-(2,4,5-trimethylphenyl)-chlorocarbonylketeneare heated at 200° C. with 4.3 g (30 mmol) of4,5-dihydro-2,2,5,5-tetramethyl-3-(2H)-furanone for 4 hours. Aftercolumn chromatography over silica gel using toluene/ethanol 20:1 as themobile phase, 4.6 g (446% of theory) of melting point: 182-184° C. areobtained.

[0733] The following compounds of the formula (I-4-a) are obtainedanalogously and in accordance with the general information on thepreparation: TABLE 8 (I-4-a)

Melting Example point No. X Y Z A D ° C. I-4-a-2 CH₃ CH₃ CH₃ —CO—(CH₂)₃—134-137 I-4-a-3 CH₃ CH₃ CH₃ CH₃ 4-F-Phenyl 216-218 I-4-a-4 CH₃ CH₃ CH₃CH₃ 2-Pyridyl 130-132 I-4-a-5 CH₃ CH₃ CH₃ CH₃

65-68 I-4-a-6 CH₃ CH₃ CH₃ CH₃ 4-Cl- 192-194 Phenyl-

Example (I-4-b-1)

[0734]

[0735] 2.5 g (7.5 mmol) of the compound (I-4-a-1) are initiallyintroduced into 25 ml of ethyl acetate, 0.75 g of triethylamine isadded, and 0.6 g of acetyl chloride in 20 ml of ethyl acetate is addeddropwise at 0° C. The mixture is stirred at room temperature for 20hours, the precipitate is separated off and the product is washed twicewith 50 ml of half-concentrated sodium chloride solution, dried oversodium sulphate and evaporated in vacuo. The residue is chromatographedover silica gel using toluene/acetone 50:1.

[0736] Yield: 0.8 g (A 29% of theory) of melting point: 143-144° C.

[0737] The compounds of the formula I-4-b listed in the following tablewere prepared analogously to Example I-4-b-1 and in accordance with thegeneral information on the preparation: TABLE 9 (I-4-b)

Melting point: [° C.] σ. Example ¹H-NMR (CDCl₃): δ No. X Y Z A D R¹[ppm] I-4-b-2 CH₃ CH₃ CH₃ CH₃ 4-F-Phenyl CH₃ 141-143 I-4-b-3 CH₃ CH₃ CH₃CH₃ 2-Pyridyl CH₃ 135-136 I-4-b-4 CH₃ CH₃ CH₃ CH₃ 2-PyridylC(CH₃)—(CH₂OCH₃)₂ 8.68(1H, d), 7.98(1H, d), 7.80(1H, t), 2.33(3H, s),2.23(3H, s), 2.20(3H, s), 2.15(3H, s) I-4-b-5 CH₃ CH₃ CH₃ CH₃

CH₃ 137-139

Example (I-4-c-1)

[0738]

[0739] 1.7 g (5 mmol) of the compound (I-4-a-3) are initially introducedinto 20 ml of ethyl acetate, 0.5 g (5 mmol) of triethylamine is added,and 0.5 g (5 mmol) of methyl chloroformate in 5 ml of ethyl acetate isadded dropwise at 0° C. The mixture is stirred at room temperature for20 hours, the precipitate is separated off and the product is washedtwice with 50 ml of half-concentrated sodium chloride solution, driedover sodium sulphate and evaporated in vacuo. The residue ischromatographed over silica gel using toluene/acetone 30/1. Yield 1.0 g(51% of theory) of melting point 144 to 146° C.

[0740] The following compounds of the formula (I-4-c) are obtainedanalogously and in accordance with the general information on thepreparation: TABLE 10 (I-4-c)

Example Melting No. X Y Z A D R² L M point ° C. I-4-c-2 CH₃ CH₃ CH₃ CH₃2-Pyridyl CH₃ O O 160-162 I-4-c-3 CH₃ CH₃ CH₃ CH₃ 2-Pyridyl CH(CH₃)—C₂H₅O O 107-109

Example (I-5-a-1)

[0741]

[0742] 2.2 g (10 mmol) of2-(2,4,5-trimethylphenyl)-chloro-carbonylketene are heated at 50° C.with 1.6 g (10 mmol) of 4-fluorothiobenzamide in 80 ml of toluene for 6hours. The precipitate is separated off, washed with cyclohexane anddried. 2.8 g (82% of theory) of melting point 215 to 216° C. areobtained.

Example (XXIII-1)

[0743]

[0744] 247 g (1.162 mol) of the compound according to Example (XXIV-1)(75% pure) are added dropwise to a mixture of 100 g (1.785 mol) of KOHin 130 ml of water and 260 ml of methanol at room temperature and themixture is heated under reflux for 5 hours. After cooling, it is dilutedwith 300 ml of water and extracted with ethyl acetate. The aqueous phaseis acidified with half-concentrated hydrochloric acid and theprecipitate is filtered off with suction and dried.

[0745] Yield: 77 g (45% of theory), melting point: 119-121° C.

Example (XXIII-2)

[0746]

[0747] 2,4,5-Trichloro-phenylacetic acid, melting point: 112-115° C., isobtained analogously to Example (XXII-1)

[0748] Preparation of 2,4,5-trimethyl-phenylacetic Acid

[0749] Me═CH₃

Example (XXIII-3)

[0750] 286 g (1.4 mol) of 66% pure 1,2,4,5-tetramethylbenzene aredissolved in 563 ml of carbon tetrachloride, and 27.5 g (0.15 mol) ofN-bromosuccinimide and 0.4 g of benzoyl chloride are introduced insuccession at room temperature. The mixture is heated to 80° C. and 248g (1.39 mol) of N-bromosuccinimide are added in portions. Thereafter,the mixture is subsequently stirred at 80° C. for a further 30 minutesand is then cooled to room temperature. The solid is filtered off withsuction and the solvent is stripped off under 20 mbar via a solidsbridge. The residue is then distilled under a high vacuum and 226 g (66%of theory) of 2,4,5-trimethylbenzyl bromide having a boiling point of95° C. under 0.05 mbar and a purity of 86% are obtained.

[0751] A solution of 226 g (0.91 mol) of 2,4,5-trimethyl-benzyl bromide(86% pure) in 94 ml of toluene is added dropwise to a solution of 57 g(1.16 mol) of sodium cyanide in 63 ml of water and 0.6 g of Aliquat 336at 60 to 80° C., and the mixture is then subsequently stirred at 80° C.for 4 hours. After cooling to room temperature, the phases are separatedand the organic phase is washed twice with water and twice withsaturated NaCl solution, dried and concentrated. After distillation, 103g (70%) of 2,4,5-trimethyl-benzyl cyanide having a purity of 99% and aboiling point of 120° C. under 0.2 mbar are obtained.

[0752] 2118 ml of concentrated sulphuric acid are added dropwise to 2662ml of water at room temperature and the solution is heated to 90° C. 355g (2.23 mol) of 2,4,5-trimethyl-benzyl cyanide are metered into thehalf-concentrated sulphuric acid at this temperature and the mixture issubsequently stirred at 100° C. for 8 hours. After cooling, the reactionmixture is poured into ice-water, while stirring vigorously, andfiltered with suction. The solid is washed several times with water andthen with petroleum ether and dried. 358 g (90% of theory) of2,4,5-trimethylphenylacetic acid having a melting point of 123-125° C.are obtained.

[0753] The novel phenyl acetic acids of formula (XXIII) listed in thefollowing Table 11 were prepared analogously to Examples (XXIII-1) and(XXIII-3) and in accordance with the general information on thepreparation: TABLE 11 (XXIII)

melting point Example No. X Y Z ° C. XXIII-4 Cl Br CH₃ 118-120 XXIII-5Cl CN CH₃ 164-169 XXIII-6 Br CH₃ Cl 123-125 XXIII-7 Br CH₃ CH₃ 122XXIII-8 CH₃ Br Cl 148-150 XXIII-9 F Cl OCH₃ XXIII-10 Cl —O—CF₂—O—115-119 XXIII-11 Cl Cl CH₃ 101 XXIII-12 CH₃ Br CH₃ 141 XXIII-13 Cl CH₃Cl 112 XXIII-14 Br —(CH₂)₃— 143 XXIII-15 Cl Cl F 118

[0754] The compounds of formula (XXIII) are novel excepted the compoundsin which X, Y, Z=CH₃ and in which X, Y, Z=Cl.

Example (XXIV-3)

[0755]

[0756] 35 g (0.143 mol) of methyl 2-chloro-4-bromo-5-methylphenylacetateand 31 g of CuCN are heated under reflux in 350 ml of dimethylformamidefor 1 day. The solvent is stripped of under vacuum, the residue ispartitioned between water and tert. butyl-methylether, the organic phaseis dried and evaporated.

[0757] Yield: 18 g.

[0758] The novel phenyl acetic acid esters of formula (XXIV) listed inTable 12 were prepared analogously to Example (XXIV). TABLE 12 (XXIV)

Example No. X Y Z physic. constant XXIV-4 Cl Br CH₃ mp.: 41-43° C.XXIV-5 Br CH₃ Cl mp.: 37-38° C. XXIV-6 Br CH₃ CH₃ Kp_(0.03 mbar)89-91°C. XXIV-7 CH₃ Br Cl Kp_(0.07 mbar)107-110° C. XXIV-8 Cl —O—CF₂—O— oilXXIV-9 Cl Cl CH₃ Kp_(0.4 mbar)89-91° C. XXIV-10 CH₃ Br CH₃Kp_(0.03 mbar)96-98° C. XXIV-11 Br —(CH₂)₃— Kp_(0.2 mbar)130-135° C.

[0759] The compounds of formula (XXIV) are novel except the compound inwhich X, Y, Z=CH₃ and in which X, Y, Z=Cl.

Example (XXIV-1)

[0760]

[0761] 700 ml of a 30% strength methanolic solution of sodium methylateare added dropwise to a solution of 347 g (0.948 mol) of the compoundaccording to Example (XXV-1) (74.3% pure) in 410 ml of methanol at roomtemperature, the mixture is heated under reflux for 5 hours and cooledto room temperature and 0.110 ml of concentrated sulphuric acid areadded dropwise. The mixture is boiled under reflux for 1 hour, themethanol is distilled off and the solid residue is taken up in water.The organic phase is separated off and the aqueous phase is extractedtwice with 1.5 l of methylene chloride. The combined organic phases aredried over Na₂SO₄ and concentrated.

[0762] Yield: 247 g of a dark oil A 92% of theory having a content of75% (gas chromatography).

Example (XXIV-2)

[0763]

[0764] Methyl 2,4,5-trichloro-phenylacetate is obtained analogously toExample (XXIV-1) as a dark oil in a yield of 95% of theory and a purityof 80% (gas chromatography).

Example (XXV-1)

[0765]

[0766] 2205 g (22.7 mol) of 1,1-dichloroethene are added dropwise to athoroughly cooled mixture of 229.7 g (2.272 mol) of tert-butyl nitriteand 254.8 g (1.775 mol) of anhydrous copper(II) chloride in 990 ml ofanhydrous acetonitrile, the mixture being kept at below 30° C. A mixtureof 232 g (1.49 mol) of 4-chloro-2,5--dimethylaniline and 1500 ml ofanhydrous acetonitrile is then added dropwise at a temperature of below30° C. The mixture is stirred at room temperature until the evolution ofgas has ended and is then poured cautiously into 6 l of 20% strength HCland extracted several times with a total of 6 l of methyl tert-butylether (MTBE). The combined organic phases are washed with 20% strengthHCl, dried and concentrated. The oil which remains is rectified.

[0767] Yield: 347 g of dark oil A 63% of theory having a content of 74%(gas chromatography).

Example (XXV-2)

[0768] 2-(2,4,5-Trichlorophenyl)-1,1,1-trichloroethane was obtainedanalogously to Example (XXV-1) in the form of a dark oil in a yield of81% of theory with a content of 78%.

[0769] The 1,1,1-trichloro-2-phenyl-ethanes of formula (XXV) listed inTable 13 were prepared analogously to Example (XXV-1) TABLE 13 (XXV)

Example No. X Y Z physic. constant XXV-3 Cl Br CH₃ mp.: 82-84° C. XXV-4Br CH₃ Cl oil* XXV-5 Br CH₃ CH₃ oil* XXV-6 CH₃ Br Cl oil* XXV-7 Cl—O—CF₂—O— oil* XXV-8 Cl Cl CH₃ mp.: 70-72° C. XXV-9 CH₃ Br CH₃ oil*XXV-10 Br —(CH₂)₃— oil 

[0770] The oils were used without further purification for thepreparation of the compounds of formula (XXIV). The compounds of formula(XXV) are novel except the compound in which X, Y, Z=Cl.

[0771] Synthesis of 2,4,5-trimethylphenylcarbonylketene

[0772] 100 g (0.56 mol) of 2,4,5-trimethylphenylacetic acid weredissolved in 230 ml of methanol, 6 ml of concentrated hydrochloric acidwere added and the mixture was heated under reflux for 10 hours. It wasthen cooled to room temperature and the methanol was removed in vacuo.The residue was stirred into a solution of 53 g of sodium carbonate,dissolved in 260 ml of water, and the organic phase was taken up in 200ml of toluene. The organic phase was separated off, dried andconcentrated and the residue was distilled. 48.6 g of methyl2,4,5-trimethylphenylacetate having a boiling point of 86° C. under 0.2mbar were obtained.

[0773] Dimethyl 2-(2,4,5-trimethylphenyl)-malonate

[0774] 18.6 g (0.62 mol, 80% pure) of sodium hydride were initiallyintroduced into 384 ml of dimethyl carbonate and the mixture was heatedto about 80° C. 48 g (0.25 mol) of methyl 2,4,5-trimethylphenylacetate,dissolved in 100 ml of dimethyl carbonate, were then added dropwise andthe mixture was heated under reflux for 4 hours. It was cooled to roomtemperature, the excess sodium hydride was destroyed with ethanol andthe mixture was then poured into 1500 ml of ice-water. A pH of 4 to 5was established with 6 N hydrochloric acid and the organic phase wastaken up in toluene. The organic phase was separated off, dried andconcentrated and the residue was employed in the next stage withoutfurther purification. 51.6 g of dimethyl2-(2,4,5-trimethylphenyl)-malonate were obtained as an oil.

[0775]¹H-NMR (CDCl₃): δ=7.12 (s, 1H); 6.98 (s, 1H); 4.84 (s, 1H); 3.75(s, 6H); 2.27 (s, 3H); 2.23 (s, 3H); 2.21 ppm (s, 3H).

[0776] 2-(2,4,5-Trimethylphenyl)-malonic Acid

[0777] 51.6 g (0.21 mol) of dimethyl 2-(2,4,5-trimethylphenyl)-malonatewere added dropwise to a mixture of 180 ml of methanol and 38.1 g (0.68mol) of potassium hydroxide, dissolved in 92 ml of water, at roomtemperature. The mixture was then heated under reflux for 5 hours andthen cooled to room temperature again and concentrated.

[0778] The residue was stirred into ice-water and the mixture was washedwith a little toluene. The aqueous solution was acidified to a pH of 1with concentrated hydrochloric acid, while cooling with ice, and theprecipitate was filtered off with suction and dried. 30.3 g of2-(2,4,5-trimethylphenyl)-malonic acid were obtained.

[0779]¹H-NMT (d₆-DMSO): δ=7.03 (s, 1H); 6.95 (s, 1H); 4.66 (s, 1H); 2.17(s, 3H); 2.16 ppm (s, 6H).

[0780] 2,4,5-Trimethylphenylchlorocarbonyl Ketene

[0781] 30 g of 2-(2,4,5-trimethylphenyl)-malonic acid were suspended in60 ml of toluene at 50 to 60° C. and 62.5 ml of thionyl chloride wereadded dropwise. The mixture was then heated at 90 to 100° C. for 15hours. It was then cooled, the volatile constituents were driven offwith an inert gas and the excess thionyl chloride was distilled off.30.6 g of 2,4,5-trimethylphenylchlorocarbonyl ketene were isolated asthe residue.

[0782]¹H-NMR (CDCl₃): δ=7.07 (s, 2H); 2.27 (s, 3H); 2.22 (s, 3H); 2.21ppm (s, 3H).

USE EXAMPLES Example A

[0783] Phaedon Larvae Test

[0784] Solvent: 7 parts by weight of dimethylformamide

[0785] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0786] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent andthe stated amount of emulsifier, and the concentrate is diluted withwater to the desired concentration.

[0787] Cabbage leaves (Brassica oleracea) are treated by being dippedinto the preparation of the active compound of the desired concentrationand are infested with mustard beetle larvae (Phaedon cochleariae), aslong as the leaves are still moist.

[0788] After the specified periods of time, the destruction in % isdetermined. 100% means that all the beetle larvae have been killed; 0%means that none of the beetle larvae have been killed.

[0789] In this test, for example, the compounds according to PreparationExamples I-4-b-1 and I-4-a-4 caused a destruction of 100% after 7 daysat an active concentration of, for example, 0.1%.

Example B

[0790] Plutella Test

[0791] Solvent: 7 parts by weight of dimethylformamide

[0792] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0793] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent andthe stated amount of emulsifier, and the concentrate is diluted withwater to the desired concentration.

[0794] Cabbage leaves (Brassica oleracea) are treated by being dippedinto the preparation of active compound of the desired concentration andare infested with caterpillars of the diamond-back moth (Plutellamaculipennis) while the leaves are still moist.

[0795] After the specified periods of time, the destruction in % isdetermined. 100% means that all the caterpillars have been killed; 0%means that none of the caterpillars have been killed.

[0796] In this test, for example, the compounds according to PreparationExamples I-1-a-1, I-1-b-2, I-1-c-1, I-4-a-3,1-4-a-1, I-4-b-1 and I-4-a-4caused a destruction of 100% after 7 days at an active compoundconcentration of, for example, 0.1%.

Example C

[0797] Spodoptera Test

[0798] Solvent: 7 parts by weight of dimethylformamide

[0799] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0800] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent andthe stated amount of emulsifier, and the concentrate is diluted withwater to the desired concentration.

[0801] Cabbage leaves (Brassica oleracea) are treated by being dippedinto the preparation of active compound of the desired concentration andare infested with caterpillars of the owlet moth (Spodoptera frugiperda)while the leaves are still moist.

[0802] After the specified periods of time, the destruction in % isdetermined. 100% means that all the caterpillars have been killed; 0%means that none of the caterpillars have been killed.

[0803] In this test, for example, the compounds according to PreparationExamples I-1-a-1, I-1-b-2, I-4-a-3,1-4-a-1,1-4-b-1 and I-4-a-4 caused adestruction of 100% after 7 days at an active compound concentration of,for example, 0.1%.

Example D

[0804] Nephotettix Test

[0805] Solvent: 7 parts by weight of dimethylformamide

[0806] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0807] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent andthe stated amount of emulsifier, and the concentrate is diluted withwater to the desired concentration.

[0808] Rice seedlings (Oryza sativa) are treated by being dipped intothe preparation of active compound of the desired concentration and areinfested with caterpillars of the rice green leafhopper (Nephotettixcincticeps) while the seedlings are still moist.

[0809] After the specified periods of time, the destruction in % isdetermined. 100% means that all the caterpillars have been killed; 0%means that none of the caterpillars have been killed.

[0810] In this test, for example, the compounds according to PreparationExamples I-2-a-2, I-2-a-3, I-2-b-4, I-2-b-5, I-1-a-1, I-1-b-2,1-1-c-1,I-1-b-1, I-1-b-3, I-1-c-2, I-1-c-3, I-4-a-3 and I-4-a-4 caused adestruction of 100% after 6 days at an active compound concentration of,for example, 0.1%.

Example E

[0811] Myzus Test

[0812] Solvent: 7 parts by weight of dimethylformamide

[0813] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0814] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent andthe stated amount of emulsifier, and the concentrate is diluted withwater to the desired concentration.

[0815] Cabbage leaves (Brassica oleracea) which are heavily infested bythe peach aphid (Myzus persicae) are treated by being dipped into thepreparation of the active compound of the desired concentration.

[0816] After the specified periods of time, the destruction in % isdetermined. 100% means that all the caterpillars have been killed; 0%means that none of the caterpillars have been killed.

[0817] In this test, for example, the compounds according to PreparationExamples I-2-a-1, I-2-b-4, I-1-b-2, I-1-b-3, I-1-c-2 and I-4-a-4 causeda destruction of 100% after 6 days at an active compound concentrationof, for example, 0.1%.

Example F

[0818] Tetranychus Test (OP-Resistant/dipping Treatment)

[0819] Solvent: 7 parts by weight of dimethylformamide

[0820] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0821] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent andthe stated amount of emulsifier, and the concentrate is diluted withwater to the desired concentration.

[0822] Bean plants (Phaseolus vulgaris) which are heavily infested bythe two-spotted spider mite (Tetranychus urticae) are treated by beingdipped into the preparation of the active compound of the desiredconcentration.

[0823] After the specified periods of time, the destruction in % isdetermined. 100% means that all the caterpillars have been killed; 0%means that none of the caterpillars have been killed.

[0824] In this test, for example, the compounds according to PreparationExamples I-2-b-2,1-2-b-1, I-1-b-2 and I-4-b-1 caused a destruction of atleast 98% after 13 days at an active compound concentration of, forexample, 0.1%.

Example G

[0825] Pre-Emergence Test

[0826] Solvent: 5 parts by weight of acetone

[0827] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0828] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent,the stated amount of emulsifier is added and the concentrate is dilutedwith water to the desired concentration.

[0829] Seeds of the test plants are sown in normal soil and, after 24hours, watered with the preparation of the active compound. It isexpedient to keep constant the amount of water per unit area. Theconcentration of the active compound in the preparation is of noimportance, only the amount of active compound applied per unit areabeing decisive.

[0830] After three weeks, the degree of damage to the plants is rated in% damage in comparison to the development of the untreated control.

[0831] The figures denote:

[0832] 0%=no action (like untreated control)

[0833] 100%=total destruction

[0834] In this test, for example, the compound according to PreparationExample I-4-a-3 caused damage of 90% to Alopecurus myosuroids, 96% toAvena fatua and 95% to Setaria viridis when applied in an amount of, forexample, 500 g/ha, coupled with good tolerance by Beta vulgaris.

Example H

[0835] Test with Fly Larvae/Development-Inhibiting Action

[0836] Test animals: All larval stages of Lucilia cuprina (OP-resistant)[pupae and adults (without contact with the active compound)]

[0837] Solvent: 35 parts by weight of ethylene glycol monomethyl ether35 parts by weight of nonylphenol polyglycol ether

[0838] To produce a suitable formulation, 3 parts by weight of activecompound are mixed with seven parts of the abovementionedsolvent/emulsifier mixture and the emulsion concentrate thus obtained isdiluted with water to the particular desired concentration.

[0839] 30 to 50 larvae per concentration are introduced onto horse-meat(1 cm³), in glass tubes, onto which 500 μl of the dilution to be testedare pipetted. The glass tubes are placed in plastic beakers, the base ofwhich is covered with beach sand, and are stored in a climaticallycontrolled room (26° C.±1.5° C., 70% relative humidity±10%). The actionis checked after 24 hours and 48 hours (larvicidal action). Afteremergence of the larvae (about 72 hours), the glass tubes are removedand perforated plastic lids are placed on the beakers. After 1½ timesthe development period (hatching of the control flies), the flies whichhave hatched and the pupae/pupae cases are counted.

[0840] The criterion for the action is the onset of death among thetreated larvae after 48 hours (larvicidal effect) or the inhibition ofhatching of adults from the pupae or the inhibition of pupae formation.The criterion for the in vitro action of a substance is the inhibitionof flea development or a halt in development before the adult stage.100% larvicidal action means that all the larvae have died after 48hours. 100% development-inhibiting action means that no adult flies havehatched.

[0841] In this test, for example, the compound according to PreparationExample I-4-a-1 caused an action of 100% at an active compoundconcentration of, for example, 1000 ppm.

Example I

[0842] Test with Boophilus microplus Resistant/SP-Resistant ParkhurstStrain

[0843] Test animals: Adult satiated females

[0844] Solvent: Dimethyl sulphoxide

[0845] 20 mg of active compound are dissolved in 1 ml of dimethylsulphoxide, and lower concentrations are prepared by dilution in thesame solvent.

[0846] The test is carried out as a 5-fold determination. 1 μl of thesolutions is injected into the abdomen and the animals are transferredto dishes and kept in a climatically controlled room. The action isdetermined via the inhibition of oviposition. 100% means that no tickhas laid.

[0847] In this test, for example, the compounds according to PreparationExamples I-4-a-1 and I-4-b-1 had an action of 100% at an active compoundconcentration of, for example, 20 μg per animal.

1. Compounds of the formula (I)

in which X represents halogen, alkyl, alkenyl, alkinyl, alkoxy,halogenoalkyl, halogenoalkoxy, cyano or nitro, Y represents hydrogen,halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy, cyano or nitro, Zrepresents halogen, alkyl, alkoxy, halogenoalkyl, halogenoalkoxy,hydroxyl, cyano, nitro or in each case optionally substituted phenoxy,phenylthio, 5- to 6-membered hetaryloxy, 5- to 6-membered hetarylthio,phenylalkyloxy or phenylalkylthio, Y and Z, together with the carbonatom to which they are bonded, represent a cyclic radical which isoptionally substituted and optionally interrupted by heteroatoms,wherein X has one of the abovementioned meanings, Het represents one ofthe groups

wherein A represents hydrogen, or represents alkyl, alkenyl,alkoxyalkyl, polyalkoxyalkyl or alkylthioalkyl which are in each caseoptionally substituted by halogen, or represents in each case saturatedor unsaturated and optionally substituted cycloalkyl or heterocyclyl, orrepresents aryl, arylalkyl or hetaryl which are in each case optionallysubstituted by halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy,cyano or nitro, B represents hydrogen, alkyl or alkoxyalkyl, or A and B,together with the carbon atom to which they are bonded, represent asaturated or unsaturated, optionally substituted carbocyclic orheterocyclic radical, D represents hydrogen, or represents an optionallysubstituted radical from the series consisting of alkyl, alkenyl,alkinyl, alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated orunsaturated cycloalkyl, saturated or unsaturated heterocyclyl,arylalkyl, aryl, hetarylalkyl or hetaryl, or A and D, together with theatoms to which they are bonded, represent a carbocyclic or heterocyclicradical which is in each case optionally substituted, G representshydrogen (a), or represents one of the groups

wherein E represents one metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl orpolyalkoxyalkyl which are in each case optionally substituted byhalogen, or represents cycloalkyl or heterocyclyl which are in each caseoptionally substituted by halogen, alkyl or alkoxy, or represents ineach case optionally substituted phenyl, phenylalkyl, hetaryl,phenoxyalkyl or hetaryloxyalkyl, R² represents alkyl alkenyl,alkoxyalkyl or polyalkoxyalkyl which are in each case optionallysubstituted by halogen, or represents in each case optionallysubstituted cycloalkyl, phenyl or benzyl, R³, R⁴ and R⁵ independently ofone another represent alkyl, alkoxy, alkylamino, dialkylamino,alkylthio, alkenylthio or cycloalkylthio which are in each caseoptionally substituted by halogen, or represent in each case optionallysubstituted phenyl, phenoxy or phenylthio, and R⁶ and R⁷ independentlyof one another represent hydrogen, or represent alkyl, cycloalkyl,alkenyl, alkoxy or alkoxyalkyl which are in each case optionallysubstituted by halogen, or represent in each case optionally substitutedphenyl or benzyl, or, together with the N atom to which they are bonded,form a cyclic radical which optionally contains oxygen or sulphur and isoptionally substituted.
 2. Compounds of the formula (I) according toclaim 1, in which X represents halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl,C₂-C₆-alkinyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy,cyano or nitro, Y represents hydrogen, halogen, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, cyano or nitro,Z represents halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl,C₁-C₄-halogenoalkoxy, hydroxyl, cyano or nitro, or phenoxy, phenylthio,thiazolyloxy, pyridinyloxy, pyrimidyloxy, pyrazolyloxy,phenyl-C₁-C₄-alkyloxy or phenyl-C₁-C₄-alkylthio which are in each caseoptionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, nitro or cyano, or Y and Z,together represent C₃-C₄-alkanediyl or C₃-C₄-alkenediyl which areoptionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy orC₁-C₄-halogenoalkyl and in which one to three members can optionally bereplaced, independently of one another, by oxygen, sulphur, nitrogen ora carbonyl group, X having one of the abovementioned meanings, Hetrepresents one of the groups

A represents hydrogen, or represents C₁-C₁₂-alkyl, C₂-C₈-alkenyl,C₁-CIO-alkoxy-C₁-C₈-alkyl, poly-C₁-C₈-alkoxy-C₁-C₈-alkyl orC₁-C₁₀-alkylthio-C₁-C₆-alkyl which are in each case optionallysubstituted by halogen, or represents C₃-C₈-cycloalkyl which isoptionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy and inwhich one or two methylene groups are optionally replaced by oxygenand/or sulphur, or represents phenyl, naphthyl, phenyl-C₁-C₆-alkyl,naphthyl-C₁-C₆-alkyl or hetaryl having 5 or 6 ring atoms and one tothree heteroatoms from the series consisting of oxygen, sulphur andnitrogen, which are in each case optionally substituted by halogen,C₁-C₆-alkyl, C₁-C₆-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy,cyano or nitro, B represents hydrogen, C₁-C₁₂-alkyl orC₁-C₈-alkoxy-C₁-C₆-alkyl or A, B and the carbon atom to which they arebonded represent C₃-C₁₀-cycloalkyl or C₅-C₁₀-cycloalkenyl, wherein onemethylene group is optionally replaced by oxygen or sulphur and whichare optionally substituted by C₁-C₈-alkyl, C₃-C₁₀-cycloalkyl,C₁-C₈-halogenoalkyl, C₁-C₈-alkoxy, C₁-C₈-alkylthio, halogen or phenyl,or A, B and the carbon atom to which they are bonded representC₅-C₆-cycloalkyl which is substituted by an alkylenediyl group whichoptionally contains one or two oxygen and/or sulphur atoms or by analkylenedioxyl group or by an alkylenedithioyl group, this substituentforming a further five- to eight-membered ring with the carbon atom towhich it is bonded, or A, B and the carbon atom to which they are bondedrepresent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl in which twosubstituents, together with the carbon atom to which they are bonded,represent C₃-C₆-alkanediyl, C₃-C₆-alkenediyl or C₄-C₆-alkadienediylwhich are in each case optionally substituted by C₁-C₆-alkyl,C₁-C₆-alkoxy or halogen and wherein in each case one methylene group isoptionally replaced by oxygen or sulphur, D represents hydrogen, orrepresents C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkinyl,C₁-C₁₀-alkoxy-C₂-C₈-alkyl, poly-C₁-C₈-alkoxy-C₂-C₈-alkyl orC₁-C₁₀-alkylthio-C₂-C₈-alkyl which are in each case optionallysubstituted by halogen, or represents C₃-C₈-cycloalkyl which isoptionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy orC₁-C₄-halogenoalkyl and in which one or two methylene groups which arenot directly adjacent are optionally replaced by oxygen and/or sulphur,or represent phenyl, hetaryl having 5 to 6 ring atoms and one or twoheteroatoms from the series consisting of oxygen, sulphur and nitrogen,phenyl-C₁-C₆-alkyl or hetaryl-C₁-C₆-alkyl having 5 to 6 ring atoms andone or two heteroatoms from the series consisting of oxygen, sulphur andnitrogen, which are in each case optionally substituted by halogen,C₁-C₆-alkyl, C₁-C₆-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy,cyano or nitro, or A and D together represent a C₃-C₆-alkanediyl,C₃-C₆-alkenediyl or C₄-C₆-alkadienediyl group in which in each case onemethylene group is optionally replaced by oxygen or sulphur and whichare in each case optionally substituted by halogen or C₁-C₁₀-alkyl,C₁-C₆-alkoxy, C₁-C₆-alkylthio, C₃-C₇-cycloalkyl, phenyl or benzyloxywhich are in each case optionally substituted by halogen, or by afurther C₃-C₆-alkanediyl, C₃-C₆-alkenediyl or C₄-C₆-alkadienediyl groupwhich forms a fused-on ring and in which in each case one methylenegroup is optionally replaced by oxygen or sulphur and which areoptionally substituted by C₁-C₆-alkyl, or A and D together represent aC₃-C₆-alkanediyl or C₃-C₆-alkenediyl group which in each case optionallycontains one of the following groups

G represents hydrogen (a), or represents one of the groups

in which E represents one metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur and M represents oxygen or sulphur, R¹represents C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl,C₁-C₈-alkylthio-C₁-C₈-alkyl or poly-C₁-C₈-alkoxy-C₁-C₈-alkyl which arein each case optionally substituted by halogen, or representsC₃-C₈-cycloalkyl which is optionally substituted by halogen, C₁-C₆-alkylor C₁-C₆-alkoxy and in which one or two methylene groups are optionallyreplaced by oxygen and/or sulphur, or represents phenyl which isoptionally substituted by halogen, cyano, nitro, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl, C₁-C₆-halogenoalkoxy, C₁-C₆-alkylthioor C₁-C₆-alkylsulphonyl, or represents phenyl-C₁-C₆-alkyl which isoptionally substituted by halogen, nitro, cyano, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl or C₁-C₆-halogenoalkoxy, or represents5- or 6-membered hetaryl having one or two heteroatoms from the seriesconsisting of oxygen, sulphur and nitrogen which is optionallysubstituted by halogen or C₁-C₆-alkyl, or represents phenoxy-C₁-C₆-alkylwhich is optionally substituted by halogen or C₁-C₆-alkyl or represents5- or 6-membered hetaryloxy-C₁-C₆-alkyl which has one or two heteroatomsfrom the series consisting of oxygen, sulphur and nitrogen and isoptionally substituted by halogen, amino or C₁-C₆-alkyl, R² representsC₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl orpoly-C₁-C₈-alkoxy-C₂-C₈-alkyl which are in each case optionallysubstituted by halogen, or represents C₃-C₈-cycloalkyl which isoptionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy, orrepresents phenyl or benzyl which are in each case optionallysubstituted by halogen, cyano, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₆-halogenoalkyl or C₁-C₆-halogenoalkoxy, R³ represents C₁-C₈-alkylwhich is optionally substituted by halogen, or phenyl or benzyl whichare in each case optionally substituted by halogen, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, cyano or nitro,R⁴ and R⁵ independently of one another represent C₁-C₈-alkyl,C₁-C₈-alkoxy, C₁-C₈-alkylamino, di-(C₁-C₈-alkyl)amino, C₁-C₈-alkylthioor C₃-C₈-alkenylthio which are in each case optionally substituted byhalogen, or represent phenyl, phenoxy or phenylthio which are in eachcase optionally substituted by halogen, nitro, cyano, C₁-C₄-alkoxy,C₁-C₄-halogenoalkoxy, C₁-C₄-alkylthio, C₁-C₄-halogenoalkylthio,C₁-C₄-alkyl or C₁-C₄-halogenoalkyl, R⁶ and R⁷ independently of oneanother represent hydrogen, or represent C₁-C₈-alkyl, C₃-C₈-cycloalkyl,C₁-C₈-alkoxy, C₃-C₈-alkenyl or C₁-C₈-alkoxy-C₂-C₈-alkyl which are ineach case optionally substituted by halogen, or represent phenyl orbenzyl which are in each case optionally substituted by halogen,C₁-C₈-alkyl, C₁-C₈-halogenoalkyl or C₁-C₈-alkoxy, or together representa C₃-C₆-alkylene radical which is optionally substituted by C₁-C₆-alkyland in which one methylene group is optionally replaced by oxygen orsulphur, R¹³ represents hydrogen, or C₁-C₈-alkyl or C₁-C₈-alkoxy whichare in each case optionally substituted by halogen, or representsC₃-C₈-cycloalkyl which is optionally substituted by halogen, C₁-C₄-alkylor C₁-C₄-alkoxy and in which one methylene group is optionally replacedby oxygen or sulphur, or represents phenyl, phenyl-C₁-C₄-alkyl orphenyl-C₁-C₄-alkoxy which are in each case optionally substituted byhalogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl,C₁-C₄-halogenoalkoxy, nitro or cyano, R¹⁴ represents hydrogen orC₁-C₈-alkyl, or R¹³ and R¹⁴ together represent C₄-C₆-alkanediyl, R¹⁵ andR¹⁶ are identical or different and represent C₁-C₆-alkyl, or R¹⁵ and R¹⁶together represent a C₂-C₄-alkanediyl radical which is optionallysubstituted by C₁-C₆-alkyl or by phenyl which is optionally substitutedby halogen, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy,C₁-C₄-halogenoalkoxy, nitro or cyano, R¹⁷ and R¹⁸ independently of oneanother represent hydrogen, or represent C₁-C₈-alkyl which is optionallysubstituted by halogen, or represent phenyl which is optionallysubstituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl,C₁-C₄-halogenoalkoxy, nitro or cyano, or R¹⁷ and R¹⁸, together with thecarbon atom to which they are bonded, represent C₅-C₇-cycloalkyl whichis optionally substituted by C₁-C₄-alkyl and in which one methylenegroup is optionally replaced by oxygen or sulphur, R¹⁹ and R²⁰independently of one another represent C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl,C₁-C₁₀-alkoxy, C₁-C₁₀-alkylamino, C₃-C₁₀-alkenyl amino,di-(C₁-C₁₀-alkyl)amino or di-(C₃-C₁₀-alkenyl)amino.
 3. Compounds of theformula (I) according to claim 1, in which X represents fluorine,chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, cyano or nitro, Y represents hydrogen, fluorine,chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, cyano or nitro, Z represents fluorine, chlorine,bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, hydroxy, cyano or nitro, or phenoxy or benzyloxywhich are in each case optionally substituted by fluorine, chlorine,bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, nitro or cyano, or Y and Z, together particularlypreferably represent C₃-C₄-alkanediyl or C₃-C₄-alkenediyl which areoptionally substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl,C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl and in which one or two memberswhich are not directly adjacent can optionally be replaced,independently of one another, by oxygen, sulphur or nitrogen, X havingone of the abovementioned meanings, Het represents one of the groups

A represents hydrogen, or represents C₁-C₁₀-alkyl, C₂-C₆-alkenyl,C₁-C₈-alkoxy-C₁-C₆-alkyl, poly-C₁-C₆-alkoxy-C₁-C₆-alkyl orC₁-C₈-alkylthio-C₁-C₆-alkyl which are in each case optionallysubstituted by fluorine or chlorine, or represents C₃-C₇-cycloalkylwhich is optionally substituted by fluorine, chlorine, C₁-C₄-alkyl orC₁-C₄-alkoxy and in which one or two methylene groups are optionallyreplaced by oxygen and/or sulphur, or represents phenyl, furanyl,pyridyl, imidazolyl, triazolyl, pyrazolyl, indolyl, thiazolyl, thienylor phenyl-C₁-C₄-alkyl which are in each case optionally substituted byfluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl,C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, cyano or nitro, B representshydrogen, C₁-C₁₀-alkyl or C₁-C₆-alkoxy-C₁-C₄-alkyl or A, B and thecarbon atom to which they are bonded represent C₃-C₈-cycloalkyl orC₅-C₈-cycloalkenyl, wherein in each case one methylene group isoptionally replaced by oxygen or sulphur and which are optionallysubstituted by C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₃-halogenoalkyl,C₁-C₆-alkoxy, C₁-C₆-alkylthio, fluorine, chlorine or phenyl, or A, B andthe carbon atom to which they are bonded represent C₅-C₆-cycloalkylwhich is substituted by an alkylenedlyl group which optionally containsone or two oxygen or sulphur atoms or by an alkylenedioxyl group or byan alkylenedithiol group, this substituent, together with the carbonatom to which it is bonded, forming a further five- to seven-memberedring, or A, B and the carbon atom to which they are bonded representC₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which two substituents,together with the carbon atom to which they are bonded, representC₃-C₅-alkanediyl, C₃-C₅-alkenediyl or butadienediyl which are in eachcase optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, fluorine,chlorine or bromine, wherein in each case one methylene group isoptionally replaced by oxygen or sulphur, D represents hydrogen, orrepresents C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkinyl,C₁-C₈-alkoxy-C₂-C₆-alkyl, poly-C₁-C₆-alkoxy-C₂-C₆-alkyl orC₁-C₈-alkylthio-C₂-C₆-alkyl which are in each case optionallysubstituted by fluorine or chlorine, or represents C₃-C₇-cycloalkylwhich is optionally substituted by fluorine, chlorine, C₁-C₄-alkyl,C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl and in which one or two methylenegroups which are not directly adjacent are optionally replaced by oxygenand/or sulphur, or represents phenyl, furanyl, imidazolyl, pyridyl,thiazolyl, pyrazolyl, pyrimidyl, pyrrolyl, thienyl, triazolyl orphenyl-C₁-C₄-alkyl which are in each case optionally substituted byfluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl,C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, cyano or nitro, or A and D togetherrepresent a C₃-C,-alkanediyl or C₃-C₅-alkenediyl group wherein in eachcase one carbon atom is optionally replaced by oxygen or sulphur andwhich are optionally substituted by fluorine, chlorine or byC₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, phenyl orbenzyloxy which are in each case optionally substituted by fluorine orchlorine, or which in each case optionally contain one of the followinggroups:

G represents hydrogen (a), or represents one of the groups

in which E represents one metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur and M represents oxygen or sulphur, R¹represents C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl,C₁-C₆-alkylthio-C₁-C₆-alkyl or poly-C₁-C₆-alkoxy-C₁-C₆-alkyl which arein each case optionally substituted by fluorine or chlorine, orrepresents C₃-C₇-cycloalkyl which is optionally substituted by fluorine,chlorine, C₁-C₅-alkyl or C₁-C₅-alkoxy and in which one or two methylenegroups are optionally replaced by oxygen and/or sulphur, or representsphenyl which is optionally substituted by fluorine, chlorine, bromine,cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₃-halogenoalkyl,C₁-C₃-halogenoalkoxy, C₁-C₄-alkylthio or C₁-C₄-alkylsulphonyl, orrepresents phenyl-C₁-C₄-alkyl which is optionally substituted byfluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₃-halogenoalkyl or C₁-C₃-halogenoalkoxy, or represents pyrazolyl,thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl which are in each caseoptionally substituted by fluorine, chlorine, bromine or C₁-C₄-alkyl, orrepresents phenoxy-C₁-C₅-alkyl which is optionally substituted byfluorine, chlorine, bromine or C₁-C₄-alkyl, or representspyridyloxy-C₁-C₅-alkyl, pyrimidyloxy-C₁-C₅-alkyl orthiazolyloxy-C₁-C₅-alkyl which are in each case optionally substitutedby fluorine, chlorine, bromine, amino or C₁-C₄-alkyl, R² representsC₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl orpoly-C₁-C₆-alkoxy-C₂-C₆-alkyl which are in each case optionallysubstituted by fluorine or chlorine, or represents C₃-C₇-cycloalkylwhich is optionally substituted by fluorine, chlorine, C₁-C₄-alkyl orC₁-C₄-alkoxy, or represents phenyl or benzyl which are in each caseoptionally substituted by fluorine, chlorine, bromine, cyano, nitro,C₁-C₄-alkyl, C₁-C₃-alkoxy, C₁-C₃-halogenoalkyl or C₁-C₃-halogenoalkoxy,R³ represents C₁-C₆-alkyl which is optionally substituted by fluorine orchlorine, or phenyl or benzyl which are in each case optionallysubstituted by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₂-halogenoalkoxy, C₁-C₂-halogenoalkyl, cyano or nitro, R⁴ and R⁵independently of one another represent C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₆-alkylamino, di-(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio orC₃-C₄-alkenylthio which are in each case optionally substituted byfluorine or chlorine, or represent phenyl, phenoxy or phenylthio whichare in each case optionally substituted by fluorine, chlorine, bromine,nitro, cyano, C₁-C₃-alkoxy, C₁-C₃-halogenoalkoxy, C₁-C₃-alkylthio,C₁-C₃-halogenoalkylthio, C₁-C₃-alkyl or C₁-C₃-halogenoalkyl, R⁶ and R⁷independently of one another represent hydrogen, or representC₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyl orC₁-C₆-alkoxy-C₂-C₆-alkyl which are in each case optionally substitutedby fluorine or chlorine, or represent phenyl or benzyl which are in eachcase optionally substituted by fluorine, chlorine, bromine,C₁-C₅-halogenoalkyl, C₁-C₅-alkyl or C₁-C₅-alkoxy, or together representa C₃-C₆-alkylene radical which is optionally substituted by C₁-C₄-alkyland in which one methylene group is optionally replaced by oxygen orsulphur, R¹³ represents hydrogen, or C₁-C₆-alkyl or C₁-C₆-alkoxy whichare in each case optionally substituted by fluorine or chlorine, orrepresents C₃-C₇-cycloalkyl which is optionally substituted by fluorine,C₁-C₂-alkyl or C₁-C₂-alkoxy and in which one methylene group isoptionally replaced by oxygen or sulphur, or represents phenyl,phenyl-C₁-C₃-alkyl or phenyl-C₁-C₂-alkyloxy which are in each caseoptionally substituted by fluorine, chlorine, bromine, C₁-C₅-alkyl,C₁-C₅-alkoxy, C₁-C₂-halogenoalkyl, C₁-C₂-halogenoalkoxy, nitro or cyano,R¹⁴ represents hydrogen or C₁-C₆-alkyl, or R¹³ and R¹⁴ togetherrepresent C₄-C₆-alkanediyl, R¹⁵ and R¹⁶ are identical or different andrepresent C₁-C₄-alkyl, or R¹⁵ and R¹⁶ together represent aC₂-C₃-alkanediyl radical which is optionally substituted by C₁-C₄-alkylor by phenyl which is optionally substituted by fluorine, chlorine,bromine, C₁-C₂-alkyl, C₁-C₂-halogenoalkyl, C₁-C₂-alkoxy,C₁-C₂-halogenoalkoxy, nitro or cyano.
 4. Compounds of the formula (I)according to claim 1, in which X represents fluorine, chlorine, bromine,methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tert-butyl,methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl,trifluoromethoxy, difluoromethoxy, cyano or nitro, Y representshydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl,iso-propyl, butyl, iso-butyl, tert-butyl, methoxy, ethoxy, propoxy,iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyanoor nitro, Z represents fluorine, chlorine, bromine, methyl, ethyl,propyl, butyl, iso-butyl, iso-propyl, tert-butyl, methoxy, ethoxy,propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy,difluoromethoxy, cyano or nitro, or Y and Z, together representC₃-C₄-alkanediyl which is optionally substituted by fluorine, chlorine,methyl, ethyl, propyl, iso-propyl, methoxy, ethoxy, propoxy, iso-propoxyor trifluoromethyl and in which two members which are not directlyadjacent are optionally replaced by oxygen, X having one of theabovementioned meanings, Het represents one of the groups

A represents hydrogen, or represents C₁-C₈-alkyl, C₂-C₄-alkenyl,C₁-C₆-alkoxy-C₁-C₄-alkyl, poly-C₁-C₄-alkoxy-C₁-C₄-alkyl orC₁-C₆-alkylthio-C₁-C₄-alkyl which are in each case optionallysubstituted by fluorine or chlorine, or represents C₃-C₆-cycloalkylwhich is optionally substituted by fluorine, chlorine, methyl or methoxyand in which one or two methylene groups are optionally replaced byoxygen and/or sulphur, or represents phenyl, pyridyl or benzyl which arein each case optionally substituted by fluorine, chlorine, bromine,methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, trifluoromethyl,trifluoromethoxy, cyano or nitro, B represents hydrogen, C₁-C₈-alkyl orC₁-C₄-alkoxy-C₁-C₂-alkyl or A, B and the carbon atom to which they arebonded represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl, wherein in eachcase one methylene group is optionally replaced by oxygen or sulphur andwhich are optionally substituted by methyl, ethyl, n-propyl, iso-propyl,butyl, iso-butyl, sec-butyl, tert-butyl, cyclohexyl, trifluoromethyl,methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy, iso-butoxy, sec-butoxy,tert-butoxy, methylthio, ethylthio, fluorine, chlorine or phenyl, or A,B and the carbon atom to which they are bonded representC₅-C₆-cycloalkyl which is substituted by an alkylenediyl group whichoptionally contains an oxygen or sulphur atom or by an alkylenedioxylgroup, this substituent forming a further five- or six-membered ringwith the carbon atom to which it is bonded, or A, B and the carbon atomto which they are bonded represent C₃-C₆-cycloalkyl orC₅-C₆-cycloalkenyl in which two substituents, together with the carbonatoms to which they are bonded, represent C₃-C₄-alkanediyl,C₃-C₄-alkenediyl or butadienediyl, wherein in each case one methylenegroup is optionally replaced by oxygen or sulphur, D representshydrogen, or represents C₁-C₈-alkyl, C₃-C₄-alkenyl, C₃-C₄-alkinyl,C₁-C₆-alkoxy-C₂-C₄-alkyl, poly-C₁-C₄-alkoxy-C₂-C₄-alkyl,C₁-C₄-alkylthio-C₂-C₄-alkyl or C₃-C₆-cycloalkyl which are in each caseoptionally substituted by fluorine or chlorine and in which one or twomethylene groups which are not directly adjacent are optionally replacedby oxygen and/or sulphur, or represent phenyl, furanyl, pyridyl, thienylor benzyl which are in each case optionally substituted by fluorine,chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy,trifluoromethyl, trifluoromethoxy, cyano or nitro, or A and D togetherrepresent a C₃-C₅-alkanediyl or C₃-C₅-alkenediyl group wherein in eachcase one methylene group is optionally replaced by oxygen or sulphur andwhich are optionally substituted by fluorine, chlorine or byC₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl, phenyl orbenzyloxy which are in each case optionally substituted by fluorine orchlorine, G represents hydrogen (a), or represents one of the groups

in which E represents one metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur and M represents oxygen or sulphur, R¹represents C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₁-C₆-alkyl,C₁-C₄-alkylthio-C₁-C₆-alkyl or poly-C₁-C₄-alkoxy-C₁-C₄-alkyl which arein each case optionally substituted by fluorine or chlorine, orrepresents C₃-C₆-cycloalkyl which is optionally substituted by fluorine,chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,tert-butyl, methoxy, ethoxy, n-propoxy or iso-propoxy and in which oneor two methylene groups are optionally replaced by oxygen and/orsulphur, or represents phenyl which is optionally substituted byfluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl,i-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy,methylthio, ethylthio, methylsulphonyl or ethylsulphonyl, or representsbenzyl which is optionally substituted by fluorine, chlorine, bromine,methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl ortrifluoromethoxy, or represents furanyl, thienyl or pyridyl which are ineach case optionally substituted by fluorine, chlorine, bromine, methylor ethyl, or represents phenoxy-C₁-C₄-alkyl which is optionallysubstituted by fluorine, chlorine, methyl or ethyl, or representspyridyloxy-C₁-C₄-alkyl, pyrimidyloxy-C₁-C₄-alkyl orthiazolyloxy-C₁-C₄-alkyl which are in each case optionally substitutedby fluorine, chlorine, amino, methyl or ethyl, R² representsC₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₂-C₆-alkyl orpoly-C₁-C₄-alkoxy-C₂-C₆-alkyl which are in each case optionallysubstituted by fluorine or chlorine, or represents C₃-C₆-cycloalkylwhich is optionally substituted by fluorine, chlorine, methyl, ethyl,n-propyl, iso-propyl or methoxy, or represents phenyl or benzyl whichare in each case optionally substituted by fluorine, chlorine, cyano,nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy,trifluoromethyl or trifluoromethoxy, R³ represents methyl, ethyl,propyl, iso-propyl, butyl or tert-butyl which are optionally substitutedby fluorine or chlorine, or phenyl or benzyl which are in each caseoptionally substituted by fluorine, chlorine, bromine, methyl, ethyl,iso-propyl, tert-butyl, methoxy, ethoxy, iso-propoxy, trifluoromethyl,trifluoromethoxy, cyano or nitro, R⁴ and R⁵ independently of one anotherrepresent C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino,di-(C₁-C₄-alkyl)amino or C₁-C₄-alkylthio which are in each caseoptionally substituted by fluorine or chlorine, or represent phenyl,phenoxy or phenylthio which are in each case optionally substituted byfluorine, chlorine, bromine, nitro, cyano, methyl, methoxy,trifluoromethyl or trifluoromethoxy, R⁶ and R⁷ independently of oneanother represent hydrogen, or represent C₁-C₄-alkyl, C₃-C₆-cycloalkyl,C₁-C₄-alkoxy, C₃-C₄-alkenyl or C₁-C₄-alkoxy-C₂-C₄-alkyl which are ineach case optionally substituted by fluorine or chlorine, or representphenyl or benzyl which are in each case optionally substituted byfluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl, ortogether represent a C₅-C₆-alkylene radical which is optionallysubstituted by methyl or ethyl and in which one methylene group isoptionally replaced by oxygen or sulphur.
 5. Process for the preparationof compounds of the formula (I) according to claim 1, characterized inthat to obtain (A) compounds of the formula (I-1-a)

in which A, B, X, Y and Z have the meanings given in claim 1, compoundsof the formula (II)

in which A, B, X, Y and Z have the meanings given in claim 1 and R⁸represents alkyl, are subjected to intramolecular condensation in thepresence of a diluent and in the presence of a base, (B) compounds ofthe formula (I-2-a)

in which A, B, X, Y and Z have the abovementioned meanings, compounds ofthe formula (III)

in which A, B, X, Y, Z and R⁸ have the abovementioned meanings, aresubjected to intramolecular condensation in the presence of a diluentand in the presence of a base, (C) compounds of the formula (I-3-a)

in which A, B, X, Y and Z have the abovementioned meanings, compounds ofthe formula (IV)

in which A, B, X, Y, Z and R⁸ have the abovementioned meanings and Wrepresents hydrogen, halogen, alkyl or alkoxy, are subjected tointramolecular cyclization, if appropriate in the presence of a diluentand in the presence of an acid, (D) compounds of the formula (I-4-a)

in which A, D, X, Y and Z have the meanings given in claim 1, compoundsof the formula (V)

in which A and D have the abovementioned meanings, or silylenol ethersthereof, of the formula (Va)

in which A and D have the abovementioned meaning and R^(8′) representsalkyl, are reacted with compounds of the formula (VI)

in which X, Y and Z have the abovementioned meanings and Hal representshalogen, if appropriate in the presence of a diluent and if appropriatein the presence of an acid acceptor, (E) compounds of the formula(I-5-a)

in which A, X, Y and Z have the abovementioned meanings, compounds ofthe formula (VII)

in which A has the abovementioned meaning, are reacted with compounds ofthe formula (VI)

in which Hal, X, Y and Z have the abovementioned meanings, ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid acceptor, and, if appropriate, the compounds thusobtained, of the formulae (I-1-b) to (I-5-b) shown above, are then(F)(α) reacted with acid halides of the formula (VIII)

in which R¹ has the meaning given in claim 1 and Hal represents halogen,or β) with carboxylic acid anhydrides of the formula (IX)R¹—CO—O—CO—R¹  (IX) in which R¹ has the abovementioned meaning, ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent, or (G) reacted with chloroformic acidesters or chloroformic acid thioesters of the formula (X)R²—M—CO—Cl  (X) in which R² and M have the meanings given in claim 1, ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid-binding agent, or (H)α) reacted withchloromonothioformic acid esters or chlorodithioformic acid esters ofthe formula (XI)

in which M and R² have the abovementioned meanings, if appropriate inthe presence of a diluent and if appropriate in the presence of anacid-binding agent, or β) reacted with carbon disulphide and then withcompounds of the formula (XII) R²-Hal  (XII) in which R² has theabovementioned meaning and Hal represents chlorine, bromine or iodine,if appropriate in the presence of a diluent and if appropriate in thepresence of a base, or (I) reacted with sulphonic acid chlorides of theformula (XIII) R³—SO₂—Cl  (XIII) in which R³ has the meaning given inclaim 1, if appropriate in the presence of a diluent and if appropriatein the presence of an acid-binding agent, or (J) reacted with phosphoruscompounds of the formula (XIV)

(XIV) in which L, R⁴ and R⁵ have the abovementioned meanings and Halrepresents halogen, if appropriate in the presence of a diluent and ifappropriate in the presence of an acid-binding agent, or (K) reactedwith metal compounds or amines of the formulae (XV) or (XVI)Me(OR¹⁰)_(t)  (XV)

in which Me represents a mono- or divalent metal, t represents thenumber 1 or 2 and R¹⁰, R¹¹ and R¹² independently of one anotherrepresent hydrogen or alkyl, if appropriate in the presence of adiluent, or (L)α) reacted with isocyanates or isothiocyanates of theformula (XVII) R⁶—N═C=L  (XVII) in which R⁶ and L have the meaningsgiven in claim 1, if appropriate in the presence of a diluent and ifappropriate in the presence of a catalyst, or β) reacted with carbamicacid chlorides or thiocarbamic acid chlorides of the formula (XVIII)

in which L, R⁶ and R⁷ have the abovementioned meanings, if appropriatein the presence of a diluent and if appropriate in the presence of anacid-binding agent.
 6. Compounds of the formula (II)

in which A, B, X, Y and Z have the meanings given in claim 1 and R⁸represents alkyl.
 7. Compounds of the formula (III)

in which A, B, X, Y and Z have the meanings given in claim 1 and R⁸represents alkyl.
 8. Compounds of the formula (XXI)

in which A, B, X, Y and Z have the meanings given in claim
 1. 9.Compounds of the formula (XXIX)

in which A, B, X, Y and Z have the meanings given in claim
 1. 10.Compounds of the formula (IV)

in which A, B, X, Y and Z have the meanings given in claim 1, R⁸represents alkyl and W represents hydrogen, halogen, alkyl or alkoxy.11. Compounds of the formula (VI)

in which X, Y and Z have the meanings given in claim 1 and Halrepresents chlorine or bromine.
 12. Compounds of the formula (XXXIII)

in which X, Y and Z have the meanings given in claim 1
 13. Compounds ofthe formula (XXXIV)

in which X, Y and Z have the meanings given in claim 1 and R⁸ representsalkyl.
 14. Pest control compositions and herbicides, characterized by acontent of at least one compound of the formula (I) according toclaim
 1. 15. Use of compounds of the formula (I) according to claim 1for controlling pests and undesirable plant growth.
 16. Method ofcontrolling pests, characterized in that compounds of the formula (I)according to claim 1 are allowed to act on pests, undesirable plantgrowth and/or their environment.
 17. Process for the preparation of pestcontrol compositions and herbicides, characterized in that compounds ofthe formula (I) according to claim 1 are mixed with extenders and/orsurface-active agents.
 18. Use of compounds of the formula (I) accordingto claim 1 for the preparation of pest control compositions andherbicides.